Curable composition and compatibilizing agent

ABSTRACT

It is an object of the present invention to provide a curable which has good storage stability and can give cured products retaining the high elongation characteristic originating from the polyether polymer and showing a high gel fraction and good weatherability. 
     Thus, the present invention provides a durable composition 
     which comprises the following two components: 
     a polyether polymer having at least one crosslinkable functional group and 
     a vinyl polymer 
     which is compatible with said polyether polymer having at least one crosslinkable functional group at a polymer terminus. 
     Further, the present invention provides a curable composition 
     which comprises the following three components: 
     a polyether polymer having at least one crosslinkable functional group, 
     a vinyl polymer incompatible with said polyether polymer and having at least one crosslinkable function group, and 
     a compatibilizing agent capable of compatibilizing said polyether polymer and said vinyl polymer with each other when added to a mixture thereof.

TECHNICAL FIELD

The present invention relates to a curable composition comprising acrosslinkable functional group-containing vinyl polymer and acrosslinkable functional group-containing polyether polymer and to acompatibilizing agent for compatibilizing the above polymers with eachother.

BACKGROUND ART

Unlike polymers obtainable by ionic polymerization or polycondensation,functional group-containing vinyl polymers, in particular functionalgroup-terminated vinyl polymers, obtain able by radical polymerizationhave scarcely been put to practical use. Among vinyl polymers,(meth)acrylic polymers have such characteristics as high weatherabilityand transparency that polyether polymers, hydrocarbon polymers orpolyester polymers cannot have, and (meth)acrylic polymers having analkenyl or crosslinking silyl group(s) on a side chain(s) are currentlyused in highly weather-resistant coating compositions and the like. Onthe other hand, it is not easy to control the polymerization of acrylicpolymers because of side reactions, and it is very difficult tointroduce a functional group into such polymers at one or both ends.

If vinyl polymers having an alkenyl group at a molecular chain terminusor termini can be obtained by a simple and easy method, it becomespossible to obtain cured products superior in cured product physicalproperties to cured products from vinyl polymers having a crosslinkinggroup(s) on a side chain(s). Therefore, a number of researchers have sofar made investigations concerning the method for the productionthereof. However, it is not easy to produce them on a commercial scale.In Japanese Kokai Publication Hei-01-247403 and Japanese KokaiPublication Hei-05-255415, for instance, there is disclosed a method ofsynthesizing alkenyl-terminated (meth)acrylic polymers which uses analkenyl group-containing disulfide as a chain transfer agent.

Japanese Kokai Publication Hei-05-262808 discloses a method ofsynthesizing alkenyl-terminated (meth)acrylic polymers which comprisessynthesizing a vinyl polymer having a hydroxyl group at each end using ahydroxyl group-containing disulfide and further utilizing the reactivityof each hydroxyl group.

Japanese Kokai Publication Hei-05-211922 discloses a method ofsynthesizing silyl group-terminated (meth)acrylic polymers whichcomprises synthesizing a vinyl polymer having a hydroxyl group at eachend using a hydroxyl group-containing polysulfide and the reactivity ofeach hydroxyl group.

These methods can hardly ensure that a desired functional group will beintroduced at each of both ends. Hence, cured products havingsatisfactory characteristics cannot be obtained. For introducing afunctional group at each of both ends without fail, a chain transferagent must be used in large amounts, and this is a problem from theproduction process viewpoint. In addition, these methods use an ordinarymethod of radical polymerization, so that it is difficult to control themolecular weight and molecular weight distribution (ratio of weightaverage molecular weight to number average molecular weight) of theproduct polymer.

In view of such a state of the art, the present inventors have so farmade a number of inventions relating to various crosslinkable functionalgroup-terminated vinyl polymers, methods of producing the same, curablecompositions comprising the same, and uses thereof (cf. Japanese KokaiPublication Hei-11-080249, Japanese Kokai Publication Hei-11-080250,Japanese Kokai Publication Hei-11-005815, Japanese Kokai PublicationHei-11-116617, Japanese Kokai Publication Hei-11-116606, Japanese KokaiPublication Hei-11-080571, Japanese Kokai Publication Hei-11-080570,Japanese Kokai Publication Hei-11-130931, Japanese Kokai PublicationHei-11-100433, Japanese Kokai Publication Hei-11-116763, Japanese KokaiPublication Hei-09-272714, and Japanese Kokai Publication Hei-09-272715,among others).

For example, vinyl polymers having a silicon-containing group comprisinghydroxyl or hydrolyzable group(s) bound to a silicon atom and capable ofcrosslinking under siloxane bond formation (herein after, suchsilicon-containing group is also referred to as “crosslinkable silylgroup”) or cured products obtain able from compositions comprising thesame are excellent in heat resistance and weatherability and can be usedin various fields of application which include, but are not limited to,sealing materials, for example sealing materials such as elastic sealingmaterials for building and construction and sealing materials forlaminated glass, electric and electronic part materials such as solarcell back sealers, electric insulating materials such as wire/cableinsulating sheath, pressure sensitive adhesive materials, adhesives,elastic adhesives, paints, powder paints, coating compositions, foamedbodies, potting materials for electric and electronic use, films,gaskets, casting materials, various molding materials, and rustproof andwaterproof sealants for end faces (cut sections) of net glass orlaminated glass.

On the other hand, polyether polymers having at least one crosslinkingsilyl group are disclosed, for example, in Japanese Kokoku PublicationSho-45-36319, Japanese Kokoku Publication Sho-46-12154, Japanese KokokuPublication Sho-46-30741 and Japanese Kokoku Publication Sho-49-32673,Japanese Kokai Publication Sho-50-156599, Japanese Kokai PublicationSho-51-73561, Japanese Kokai Publication Sho-54-6096, Japanese KokaiPublication Sho-55-13767, Japanese Kokai Publication Sho-55-13768,Japanese Kokai Publication Sho-55-82123, Japanese Kokai PublicationSho-55-123620, Japanese Kokai Publication Sho-55-125121, Japanese KokaiPublication Sho-55-131021, Japanese Kokai Publication Sho-55-131022,Japanese Kokai Publication Sho-55-135135 and Japanese Kokai PublicationSho-55-137129, and Japanese Kokai Publication Hei-03-72527 and JapaneseKokai Publication Hei-03-97825. When cured, they give high elongationcured products and therefore are used in elastic sealing materials andthe like mainly intended for use in building and construction.

However, these polyethers, in particular polyethers having a main chaincomprising a polypropylene oxide, have a problem in that hydrogen atomseach bound to a tertiary carbon atom are readily oxidized, hence theweatherability becomes poor, if no antioxidant is used. To solve thisproblem, the present inventors have already proposed, in Japanese KokokuPublication Hei-02-42367 and Japanese Kokoku Publication Hei-02-44845, acurable composition improved in weatherability as a result of blendingan acrylic polymer having at least one crosslinkable silyl group with apolyether polymer having at least one crosslinkable silyl group.Further, Japanese Kokoku Publication Hei-04-69667, there is disclosed asealing material composition comprising a blend of an acrylic polymerhaving an alkoxysilyl group at each of both molecular ends as producedby using a chain transfer agent with a polyether polymer having analkoxysilyl group at each of both molecular ends.

That vinyl polymer having at least one crosslinkable functional groupwhich is to be blended with the polyether polymer having at least onecrosslinkable functional group is generally produced by using acrosslinkable functional group-containing radical polymerizationinitiator or chain transfer agent. Therefore, it is difficult to attaina high percentage of crosslinkable functional group introduction at bothends. As a result, there arises a problem, namely the gel fraction ofcured products decreases.

On the other hand, the combined use of a crosslinkable functionalgroup-containing monomer is required for obtaining cured products with asatisfactory gel fraction. In this case, a problem arises, namely thehigh elongation characteristics intrinsic in polyether polymers areimpaired. In this case, the elongation at break, in particular,decreases and, accordingly, the range of application of the compositionin question is drastically restricted. Therefore, in using the same as asealing material, improvements in weatherability can be attained only bysacrificing some or other physical characteristic(s), for exampleincrease in modulus, decrease in elongation, worsening of residual tack,decrease in gel fraction, etc. In addition, the (meth)acrylic polymerused there is a product synthesized by free radical polymerization and,therefore, has a broad molecular weight distribution and a highviscosity, causing a problem that the mixture thereof with a polyetherpolymer also shows a high viscosity.

Concerning this problem, Japanese Kokai Publication Hei-11-116763proposes to obtain a curable composition high in gel fraction andexcellent in weatherability, without impairing the high elongationcharacteristic intrinsic in a crosslinkable functional group-containingpolyether polymer, by using a low-viscosity vinyl polymer having aterminal crosslinkable functional group introduced thereinto with a highpercentage. In this case, however, the compatibility of the two polymersmay be poor in certain instances according to the molecular weight andmolecular weight distribution of the vinyl polymer and/or polyetherpolymer and to the blending ratio of these two polymers. In that case,the curable composition resulting from blending, when stored for a longperiod of time, may undergo phase separation, for instance, hence thestorage stability thereof may deteriorate. Furthermore, cured productsobtainable from a composition with insufficient compatibility areinferior in homogeneity, so that good mechanical and physical propertiesmay not be realized.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a curablecomposition which comprises a crosslinkable functional group-containingvinyl polymer and a crosslinkable functional group-containing polyetherpolymer and which has good storage stability and can give cured productsretaining the high elongation characteristic originating from thepolyether polymer and showing a high gel fraction and goodweatherability.

Thus, the present invention provides a curable composition

which comprises the following two components:

(I) a polyether polymer having at least one crosslinkable functionalgroup and(II) a vinyl polymer

which is compatible with said polyether polymer, has a weight averagemolecular weight (Mw)-to-number average molecular weight (Mn) ratio(Mw/Mn) of less than 1.8 as determined by gel permeation chromatographyand has at least one crosslinkable functional group at a polymerterminus.

The present invention also provides a curable composition

which comprises the following two components:

(I) a polyether polymer having at least one crosslinkable functionalgroup and(II) a vinyl polymer

which is compatible with said polyether polymer, is a product of livingradical polymerization and has at least one crosslinkable functionalgroup at a polymer terminus.

Further, the present invention provides a curable composition

which comprises the following three components:

(I) a polyether polymer having at least one crosslinkable functionalgroup,(II) a vinyl polymer incompatible with said polyether polymer and havingat least one crosslinkable function group, and(III) a compatibilizing agent produced by copolymerization of aplurality of vinyl monomers and capable of compatibilizing saidpolyether polymer and said vinyl polymer with each other when added to amixture thereof.

Furthermore, the present invention provides a curable composition

which comprises the following three components:

(I) a polyether polymer having at least one crosslinkable functionalgroup,(II) a vinyl polymer incompatible with said polyether polymer and havingat least one crosslinkable function group, and(IV) at least one compatibilizing agent capable of compatibilizing saidpolyether polymer, and said vinyl polymer with each other when added toa mixture thereof, said compatibilizing agent being selected from thegroup consisting of nonpolymer organic compounds, polymers obtain ableby polymerizing a monomer or monomers other than vinyl monomers, andpolymers obtain able by polymerizing a single vinyl monomer.

Further, the present invention provides a compatibilizing agent obtainable by copolymerization of a plurality of vinyl monomers and capable ofcompatibilizing the two components:

(I) a polyether polymer having at least one crosslinkable functionalgroup, and(II) a vinyl polymer incompatible with said polyether polymer and havingat least one crosslinkable function group, with each other, when addedto a mixture thereof.

In the following, the present invention is described in detail.

DETAILED DISCLOSURE OF THE INVENTION <<Re: Polyether Polymer (I)>>

The component (I) in the present invention, namely the polyether polymerhaving at least one crosslinkable functional group may contain, or maynot contain, a urethane bond or urea bond in the main chain thereof. Themain chain of the polyether polymer is not particularly restricted butincludes, among others, polyethylene oxide, polypropylene oxide,polybutylene oxide, and polyphenylene oxide. Among these, those whichare essentially polyalkylene oxides are preferred, and the one which isessentially polypropylene oxide is more preferred. The latter maycontain ethylene oxide, butylene oxide, phenylene oxide or the like, inaddition to propylene oxide. The expression “the main chain isessentially polypropylene oxide” means that propylene oxide unitsaccount for at least 50%, preferably at least 70%, more preferably atleast 90%, of all the main chain-constituting repeating units. Thepolypropylene oxide polymer preferably has a molecular weightdistribution (Mw/Mn) of not more than 1.5, since a lower viscosity meansbetter handleability.

The crosslinkable functional group in component (I) is not particularlyrestricted but includes, as preferred species, crosslinkable silylgroups, alkenyl groups, a hydroxyl group, an amino group, and groupshaving a polymerizable carbon-carbon double bond, and an epoxy group,among others. In particular, crosslinkable silyl groups are preferred.The definitions of these are the same as mentioned later herein. Thecrosslinkable functional group in component (I) may be the same as ordifferent from the crosslinkable functional group in component (II).From the curability viewpoint, however, it is preferred that both be notdifferent in kind. Even when both are of the same kind, they may be thesame or different in structure. The number of crosslinkable functionalgroups which the polyether polymer (I) has is at least 1 on average, butfrom the viewpoint of the curability of the composition, it ispreferably more than 1, more preferably 1.1 to 4.0 on average, stillmore preferably 1.5 to 2.5 on average. From the viewpoint of the rubberelasticity of the cured product, the crosslinkable functional group ispreferably located at a polyether polymer terminus, more preferably ateach of the polymer termini.

The method of producing the component (I) polyether polymer is notparticularly restricted but may be any of those known in the art.

In cases where the component (I) polyether polymer having at least onecrosslinkable functional group, which is to be used in accordance withthe present invention, contains a urethane or urea bond in the mainchain thereof, any polyether polymer obtain able by any method ofproduction may be used as the component (I) provided that it is anorganic polymer containing one or more urethane or urea bonds within themolecule and having at least one crosslinkable functional group. Thecrosslinkable functional group is not particularly restricted butincludes such various functional groups as mentioned above. Preferredamong them are, however, silicon-containing groups represented by theformula (1):

—SiY_(a)R¹ _(3-a)  (1)

wherein, R¹ is an alkyl group containing 1 to 20 carbon atoms, an arylgroup containing 6 to 20 carbon atoms, an aralkyl group containing 7 to20 carbon atoms or a triorganosiloxy group represented by R′₃SiO— (inwhich R′ is a univalent hydrocarbon group containing 1 to 20 carbonatoms and the three R′ groups may be the same or different) and, whenthere are two or more R¹ groups, they may be the same or different; Yrepresents a hydroxyl group or a hydrolyzable group and, when there aretwo or more Y groups, they may be the same or different; a represents 0,1, 2 or 3. Further, use may be made of polyether polymers produced byindustrially easy and simple processes, for example the processcomprising reacting the terminal hydroxyl groups of a hydroxylgroup-terminated oxyalkylene polymer (D) with a polyisocyanate compound(E) in excess to give a polymer having an isocyanato group-terminatedpolyurethane main chain (F) and then reacting the isocyanato groups withthe W group of a silicon compound (G) represented by the formula (2):

W—R²—SiY_(a)R¹ _(3-a)  (2)

wherein R¹, Y and a are the same as defined above, R² is a substitutedor unsubstituted bivalent organic group containing 1 to 20 carbon atomsand W is an active hydrogen atom-containing group selected from amonghydroxyl, carboxyl, mercapto and amino (primary or secondary), orreacting the terminal hydroxyl group of (D) simultaneously with excess(E) and the W group of (G), or the process comprising reacting thehydroxyl group-terminated oxyalkylene polymer (D) with a hydrolyzablesilyl group-containing isocyanate compound (H) represented by theformula (3):

O═C═N—R²—SiY_(a)R¹ _(3-a)  (3)

wherein R¹, R², Y and a are the same as defined above.

The oxyalkylene polymer (D) may be any one produced by any process butpreferably is one having at least 0.7 hydroxyl groups per molecularterminus on the average for all molecules. More specifically, mentionmay be made of conventional oxyalkylene polymers produced by using analkali metal catalyst and oxyalkylene polymers produced by reacting suchan initiator as a polyhydroxy compound having at least two hydroxylgroups with an alkylene oxide in the presence of a double metal cyanidecomplex (c) or cesium, among others.

Preferred among others is the use of a double metal cyanide complex (c)since oxyalkylene polymers (D) lower in degree of unsaturation, higherin molecular weight, narrower in Mw/Mn, lower in viscosity and higher inacid resistance and weatherability can be obtained as compared with theconventional oxyalkylene polymers produced by using an alkali metalcatalyst.

Preferred as the double metal cyanide complex (C) are complexes whosemain component is zinc hexacyanocobaltate, and ethers and/or alcoholcomplexes thereof are preferred. The composition thereof may be the oneessentially described in Japanese Kokoku Publication Sho-46-27250.Preferred as the ether are tetra hydrofuran, glymes, diglymes and otherglymes. Among them, tetra hydrofuran and glymes are preferred sinceoxyalkylene polymers (D) narrower in Mw/Mn and lower in degree ofunsaturation can be obtained using them. Preferred as the alcohol ist-butanol, which is described in Japanese Kokai PublicationHei-04-145123, since oxyalkylene polymers (D) lower in degree ofunsaturation can be obtained using the same.

For attaining a high molecular weight by the reaction with thepolyisocyanate compound (E) and for increasing a high rate of silylgroup introduction by the reaction with the hydrolyzable silylgroup-containing isocyanate compound (H), the number of hydroxyl groupsin the oxyalkylene polymer (D) is preferably not less than 1.6, morepreferably 1.8 to 4, per molecule on the average for all molecules. Mostpreferably, it is 1.8 to 3 so that gelation may be avoided in the stepof reaction with the polyisocyanate compound (E). Oxyalkylene polymers(D) having at least 2 hydroxyl groups can be produced by using atrifunctional or higher functionality initiator in lieu of a part or thewhole of the bifunctional initiator. It is also possible to obtain anoxyalkylene polymer (D) having 1.8 to 3 hydroxyl groups per molecule onthe average for all molecules by blending an oxyalkylene polymer whichis at least bifunctional with an oxyalkylene polymer which is at mostbifunctional.

As specific species, there may be mentioned polyoxyethylene compounds,polyoxypropylene compounds, polyoxybutylene compounds, polyoxyhexylenecompounds, polyoxytetramethylene compounds and/or copolymers of these.

Polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene tetraol,copolymers of these polymers with ethylene oxide and, further, mixturesthereof are particularly preferred as the oxyalkylene polymer (D).

Oxyalkylene polymers obtain able by copolymerizing ethylene oxide sothat they may terminate at primary hydroxyl groups are preferred sincetheir reaction with the polyisocyanate compound (E) or hydrolyzablesilyl group-containing isocyanate compound (H) is facilitated.

The number average molecular weight of the oxyalkylene polymer (D) to beused may be not less than 1,000 but preferably is not less than 4,000,since when it is less than 4,000, the number of urethane bondsintroduced in the polyurethane main chain (F) becomes increased, so thatthe viscosity becomes relatively high.

The polyisocyanate compound (E) to be used in obtaining the polyurethanemain chain (F) may be any polyisocyanate compound.

The number of isocyanato groups contained in the polyisocyanate compound(E) is preferably 2 to 5 per molecule on average and, from the readyavailability viewpoint, it is more preferably 2 to 3. Most preferably,it is 2 since no gelation is caused on the occasion of reaction with theoxyalkylene polymer (D).

As specific examples, there may be mentioned tolylene diisocyanate(TDI), methylene diisocyanate (MDI), xylylene diisocyanate (XDI),isophoronediisocyanate (IPDI), hexamethylene diisocyanate (HMDI),tetramethylene diisocyanate (TMDI) and the like. Uretdione derivatives,isocyanurate derivatives, cyanurate derivatives or carbodiimidederivatives of these may also be used.

As specific examples of the silicon compound (G) represented by theformula (2), which is to be used for introducing the silyl grouprepresented by the formula (1) into the polyether polymer molecules,there may be mentioned amino-substituted alkoxysilanes such asγ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropyltriethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysialne and1,3-diaminoisopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane,γ-mercaptopropyltrimethoxysilane, and the like.

As specific examples of the silyl group-containing isocyanate compound(H) represented by the formula (3), which is to be used for introducingthe silyl group represented by the formula (1) into the polyetherpolymer molecules, there may be mentioned γ-trimethoxysilylpropylisocyanate, γ-triethoxysilylpropyl isocyanate,γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropylisocyanate, and the like.

A catalyst may be used in the reaction of the hydroxyl groups of theoxyalkylene polymer (D) with the isocyanato group, and in the reactionof the W group of the silicon compound with the isocyanato group. Incases where the storage stability of the resulting polyether polymer issacrificed, the reactions are preferably carried out in the absence ofany catalyst. When a catalyst is used, any of the knowncatalysts-catalyzing the reaction between a hydroxyl group and anisocyanato group may be used.

When, in the practice of the present invention, the polyether polymerhaving at least one crosslinkable functional group, which is thecomponent (I), contains a urethane or urea bond(s) in the main chainthereof, the polyether polymer preferably has a number average molecularweight of not less than 7,500. The use of such an organic polymer havinga number average molecular weight of 7,500 to 25,000 is more preferred.If the number average molecular weight of the polyether polymer is lowerthan 7,500, the cured products will become hard and low in elongationand, when the number average molecular weight exceeds 25,000, theadhesiveness of the polymer itself decreases markedly, rendering thepolymer less practicable, although there is no problem about theflexibility or elongation of the cured products. From the viscosityviewpoint, a number average molecular weight of 8,000 to 20,000 isparticularly preferred.

The mixing ration of the component (II) vinyl polymer to the component(I) polyether polymer is preferably within the range of 100/1 to 1/100,more preferably 100/5 to 5/100, still more preferably 100/10 to 10/100.When the blending proportion of the vinyl polymer (II) is smaller, theweatherability, one of the effects of the present invention, may hardlybe expressed in certain instances.

<<Re: Vinyl Polymer (II)>> <Main Chain>

The present inventors have so far made a number of inventions relatingto various crosslinkable functional group-terminated vinyl polymers,methods of producing the same, curable compositions comprising the sameand uses thereof (see, for example, Japanese Kokai PublicationHei-11-080249, Japanese Kokai Publication Hei-11-080250, Japanese KokaiPublication Hei-11-005815, Japanese Kokai Publication Hei-11-116617,Japanese Kokai Publication Hei-11-116606, Japanese Kokai PublicationHei-11-080571, Japanese Kokai Publication Hei-11-80570, Japanese KokaiPublication Hei-11-130931, Japanese Kokai Publication Hei-11-100433,Japanese Kokai Publication Hei-11-116763, Japanese Kokai PublicationHei-09-272714 and Japanese Kokai Publication Hei-09-272715). The vinylpolymer (II) to be used according to the present invention is notparticularly restricted. Thus, all the polymers disclosed in theabove-cited publications can appropriately be used. The term“compatible” as used herein refers to the condition that two or morepolymers can be sufficiently mixed up and, after one week of standing atroom temperature, the mixture will not show any boundary observable bythe eye.

The vinyl monomer constituting the main chain of the vinyl polymer (II)according to the invention is not particularly restricted but includesvarious species. As examples, there may be mentioned (meth)acrylicmonomers such as (meth)acrylic acid, methyl (meth)acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl(meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, phenyl(meth)acrylate, toluoyl (meth)acrylate, benzyl (meth)acrylate,2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate,2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl(meth)acrylate, 2-aminoethyl (meth)acrylate,γ-(methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid-ethyleneoxide adducts, trifluoromethylmethyl (meth)acrylate,2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl(meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate,2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate,diperfluoromethylmethyl (meth)acrylate,2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate; aromaticvinyl monomers such as styrene, vinyltoluene, α-methylstyrene,chlorostyrene, styrenesulfonic acid and salts thereof;fluorine-containing vinyl monomers such as perfluoroethylene,perfluoropropylene, and vinylidene fluoride; silicon-containing vinylmonomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleicanhydride, maleic acid, and maleic acid monoalkyl esters and dialkylesters; fumaric acid, and fumaric acid monoalkyl esters and dialkylesters; maleimide monomers such as maleimide, methylmaleimide,ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, andcyclohexylmaleimide; acrylonitrile monomers such as acrylonitrile andmethacrylonitrile; amide group-containing vinyl monomers such asacrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinylpropionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenessuch as ethylene and propylene; conjugated dienes such as butadiene andisoprene; vinyl chloride, vinylidene chloride, allyl chloride, allylalcohol, and the like. These may be used singly or a plurality of themmay be subjected to copolymerization.

The main chain of the vinyl polymer (II) is preferably one produced bypolymerizing mainly at least one monomer selected from the groupconsisting of (meth)acrylic monomers, acrylonitrile monomers, aromaticvinyl monomers, fluorine-containing vinyl monomers, andsilicon-containing vinyl monomers. The term “mainly” as used hereinmeans that the above-mentioned monomer accounts for at least 50 molepercent, preferably at least 70 mole percent, of the monomer unitsconstituting the vinyl polymer.

From the viewpoint of physical properties of products, among others,aromatic vinyl monomers and (meth)acrylic monomers are preferred amongothers. Acrylic ester monomers and methacrylic ester monomers are morepreferred, and acrylic ester monomers are particularly preferred. Butylactylate is still more preferred. In the practice of the presentinvention, these preferred monomers may be copolymerized or, furtherblock-copolymerized with another monomer and, on that occasion, thecontent of these preferred monomers is preferably 40% by weight. In sucha sense, the vinyl polymer (II) is preferably a (meth)acrylic polymer,more preferably an acrylic polymer, still more preferably an acrylicester polymer. In the above form of expression, “(meth)acrylic acid”,for instance, means acrylic acid and/or methacrylic acid.

From the physical properties viewpoint, in particular, the vinyl polymer(II) preferably contains (meth)acrylic ester units (a) having, in theester moiety, a group selected from the group consisting of alkyl groupscontaining 5 to 30 carbon atoms, aryl group containing 6 to 30 carbonatoms and aralkyl groups containing 7 to 30 carbon atoms. When thenumber of carbon atoms is 5 or less, the compatibility with thepolyether polymer (I) can hardly be secured and, when it is greater than30, the polymer becomes difficult to handle. More preferred as the estermoiety are alkyl, aryl or aralkyl groups containing 8 to 30 carbonatoms. Still more preferred as the ester moiety are alkyl, aryl oraralkyl groups containing 10 to 25 carbon atoms.

Especially preferred as the (meth)acrylic ester polymers are thoseresulting from copolymerization of two or more (meth)acrylic estermonomers differing in the number of carbon atoms in the ester moiety.More specifically, there may be mentioned copolymers derived from (a) a(meth)acrylic ester unit having, in their ester moiety, a group selectedfrom the group consisting of the above-mentioned C₅₋₃₀ alkyl groups,C₆₋₃₀ aryl groups and C₇₋₃₀ aralkyl groups and (b) a (meth)acrylic esterunit having, in their ester moiety, an alkyl group containing 1 to 6carbon atoms (the number of carbon atoms in the ester moiety in unit (a)being larger than the number of carbon atoms in the ester moiety in unit(b)). The mole ratio between both units is not particularly restrictedbut may be adjusted in various ways according to the physical propertiesdesired of the curable composition or cured products. Generally,however, the ratio is generally 1:100 to 100:1, preferably 1:50 to 10:1,more preferably 1:20 to 1:1.

The molecular weight distribution, namely the ratio (Mw/Mn) between theweight average molecular weight (MW) and number average molecular weight(Mn) as determined by gel permeation chromatography, of the vinylpolymer (II) according to the invention is not particularly restrictedbut preferably is less than 1.8, preferably not more than 1.7, morepreferably not more than 1.6, still more preferably not more than 1.5,especially preferably not more than 1.4, most preferably not more than1.3. In the practice of the present invention, the GPC measurement isgenerally carried out on a polystyrene gel column using chloroform as amobile phase, and the number average molecular weight can be determinedon the polystyrene equivalent basis.

The number average molecular weight of the vinyl polymer (II) accordingto the invention is not particularly restricted but preferably is notless than 3,000, more preferably not less than 5,000, still morepreferably not less than 10,000, as determined by gel permeationchromatography. When the molecular weight is lower, the high elongationrequired of the cured products may not be attained in certain instances.Further, it is preferably not more than 1,000,000, more preferably notmore than 100,000, still more preferably not more than 50,000, asdetermined by the same method.

<Method of Main Chain Synthesis>

Although the method of synthesizing the vinyl polymer (II) according tothe invention is not restricted, controlled radical polymerization ispreferred, living radical polymerization is more preferred, and atomtransfer radical polymerization is particularly preferred. These areexplained in the following.

Controlled Radical Polymerization

Radical polymerization methods can be classified into “ordinary radicalpolymerization methods” which comprise merely copolymerizing a monomerhaving a specific functional group and a vinyl monomer (s) using an azocompound, a peroxide or the like as a polymerization initiator, and“controlled radical polymerization methods” by which a specificfunctional group can be introduced into a controlled site (s), forexample a terminus or termini.

“ordinary radical polymerization methods” are simple and easy to performbut allow the specific functional group-containing monomer to beintroduced into the polymer only at random. For obtaining polymers witha high percentage of functionalization, it is necessary to use thismonomer in fairly large amounts. When, conversely, only a small amountof the monomer is used, the problem arises that the proportion ofpolymer molecules formed without introduction of this specificfunctional group increases. Further, since they consist in free radicalpolymerization, there is another problem, namely only polymers with awide molecular weight distribution and a high viscosity can be obtained.

“Controlled radical polymerization methods” can be further classifiedinto “chain transfer agent methods” which comprise carrying outpolymerization using a chain transfer agent having a specific functionalgroup(s) to give functional group-terminated vinyl polymers and “livingradical polymerization methods” by which growing polymer termini cangrow, without undergoing termination and like reactions, to givepolymers with a molecular weight approximately as designed.

“Chain transfer agent methods” can give polymers with a high level offunctionalization but require the use of a fairly large amount of achain transfer agent having a specific functional group(s) relative tothe initiator, hence have economical problems, inclusive oftreatment-related problems. Like the above-mentioned “ordinary radicalpolymerization methods”, there is also the problem that only polymershaving a wide molecular weight distribution and a high viscosity can beobtained because of their consisting in free radical polymerization.

Unlike these polymerization methods, “living radical polymerizationmethods” hardly undergo termination reactions and can give polymers witha narrow molecular weight distribution (Mw/Mn being about 1.1 to 1.5)and make it possible to arbitrarily control the molecular weight bychanging the monomer-to-initiator charge ratio, in spite of theirbelonging to the class of radical polymerization methods regarded asbeing difficult to control because of high rates of polymerization and atendency toward ready occurrence of termination reactions, such asradical-to-radical coupling.

Therefore, such “living radical polymerization methods” are morepreferred as the methods of producing the specific functionalgroup-containing vinyl polymers mentioned above, since they can givepolymers narrow in molecular weight distribution and low in viscosityand, in addition, make it possible to introduce specific functionalgroup-containing monomers into the polymers at almost arbitrarypositions.

The term “living polymerization”, in its narrow sense, means a mode ofpolymerization in which molecular chains grow while their terminus ortermini always retain activity. In the ordinary sense, however, the termalso includes the mode of pseudo-living polymerization in whichmolecular chains grow while terminally inactivated ones and terminallyactivated ones are in equilibrium. The latter definition applies also inthe present invention.

In recent years, “living radical polymerization methods” have activelybeen studied by a number of groups of researchers or example, there maybe mentioned the one using a cobalt porphyrin complex, as described inthe Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994,vol. 116, page 7943, the one using a radical capping agent, such as anitroxide compound, as described in Macromolecules, 1994, vol. 27, page7228, and “atom transfer radical polymerization” (ATRP) using an organichalide or the like as an initiator and a transition metal complex as acatalyst.

Among the “living radical polymerization methods”, the “atom transferradical polymerization method”, by which vinyl monomers are polymerizedusing an organic halide or halogenated sulfonyl compound, for instance,as an initiator and a transition metal complex as a catalyst, is morepreferred for the production of specific functional group-containingvinyl polymers, for this method not only has the characteristic featuresof “living radical polymerization” but also gives polymers having aterminal halogen atom(s) relatively convenient for functional groupconversion reactions and, further, the degree of freedom is large ininitiator and catalyst designing. As examples of this atom transferradical polymerization, there may be mentioned those described inMatyjaszewski et al.: J. Am. Chem. Soc., 1995, vol. 117, page 5614,Macromolecules, 1995, vol. 28, page 7901, Science, 1996, vol. 272, page866, WO 96/30421, WO 97/18247, WO 98/01480, WO 98/40415 and Sawamoto etal.: Macromolecules, 1995, vol. 28, page 1721, Japanese KokaiPublication Hei-09-208616 and Japanese Kokai Publication Hei-08-41117,among others.

Which of such living radical polymerization methods is to be used is notcritical in the practice of the present invention. Preferred, however,is the atom transfer radical polymerization.

In the following, this living radical polymerization is described indetail. Prior thereto, one mode of controlled radical polymerization,namely polymerization using a chain transfer agent, which can be used inproducing the polymer (II) to be described later herein, is firstdescribed. The radical polymerization using a chain transfer agent(telomer) is not particularly restricted but includes, for example, thefollowing two methods for producing vinyl polymers having a terminalstructure(s) suited for utilization in the practice of the presentinvention.

One method is to produce halogen-terminated polymers by using ahalogenated hydrocarbon as a chain transfer agent, as described inJapanese Kokai Publication Hei-04-132706, and the other is to producehydroxyl-terminated polymers using a hydroxyl-containing mercaptan or ahydroxyl-containing polysulfide or the like as a chain transfer agent,as described in Japanese Kokai Publication Sho-61-271306, JapanesePatent No. 2594402 or Japanese Kokai Publication Sho-54-47782.

The living radical polymerization is now described.

First, the technique which uses a radical capping agent such as anitroxide compound is described. In this polymerization, a nitroxy freeradial (═N—O.), which is generally stable, is used as a radical cappingagent. Such compound includes, as preferred species, but is not limitedto, 2,2,6,6-tetrasubstituted-1-piperidinyloxy radicals,2,2,5,5-tetrasubstituted-1-pyrrolidinyloxy radicals and like cyclichydroxyamine-derived nitroxy free radicals. Suitable as the substituentare alkyl groups containing not more than 4 carbon atoms, such as methylor ethyl. Specific nitroxy free radical compounds include, but are notlimited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO),2,2,6,6-tetraethyl-1-piperidinyloxy radical,2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical,2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical,1,1,3,3-tetramethyl-2-isoindolinyloxy radical andN,N-di-t-butylamine-oxy radical. It is also possible to use other stablefree radicals, such as galvinoxyl free radical, in lieu of nitroxy freeradicals.

The above radical capping agent is used in combination with a radicalformer or generator. Presumably, a reaction product formed from theradical capping agent and radical generator serves as a polymerizationinitiator to allow the polymerization of an addition-polymerizablemonomer(s) to proceed. Although the ratio between both is notparticularly restricted, the radical initiator is used appropriately inan amount of 0.1 to 10 moles per mole of the radical capping agent.

While various compounds can be used as the radical generator, a peroxidecapable of generating a radical under polymerization temperatureconditions is preferred. Such peroxide includes, but is not limited to,diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkylperoxides such as dicumyl peroxide and di-t-butyl peroxide,peroxycarbonates such as diisopropyl peroxydicarbonate andbis(4-t-butylcyclohexyl) peroxydicarbonate, and alkyl peresters such ast-butyl peroxyoctoate and t-butyl peroxybenzoate. In particular, benzoylperoxide is preferred. Further, other radical generators, for exampleradical-generating azo compounds such as azobisisobutyronitrile can beused in lieu of peroxides.

Alkoxyamine compounds such as those illustrated below may be used asinitiators in lieu of the combined use of a radical capping agent and aradical generator, as reported in Macromolecules, 1995, vol. 28, page2993.

When an alkoxyamine compound is used as an initiator and that compoundis one having a functional group, such as a hydroxyl group, such as theone illustrated above, functional group-terminated polymers areobtained. When this is utilized in the practice of the presentinvention, functional group-terminated polymers can be obtained.

The polymerization conditions, including monomer(s), solvent andpolymerization temperature, to be used in the above-mentionedpolymerization using a radical capping agent, such as a nitroxidecompound are not particularly restricted but may be the same as thoseused in the atom transfer radical polymerization mentioned below.

Atom Transfer Radical Polymerization

Now, the atom transfer radical polymerization method, which is morepreferred as the living radical polymerization in carrying out thepresent invention, is described.

In this atom transfer radical polymerization, an organic halide, inparticular a highly reactive carbon-halogen bond-containing organichalide (e.g. a carbonyl compound having a halogen at an α-position or acompound having a halogen at a benzyl position), a halogenated sulfonylcompound or the like is used as an initiator.

Specific examples are as follows:

C₆H₅—CH₂X, C₆H₅—C(H)(X)CH₃, C₆H₅—C(X)(CH₃)₂

(in the above chemical formulas, C₆H₅ is a phenyl group and X is achlorine, bromine or iodine atom);R³—C(H)(X)—CO₂R⁴, R³—C(CH₃)(X)—CO₂R⁴, R³—C(H)(X)—C(O)R⁴,

R³—C(CH₃)(X)—C(O)R⁴

(in the above formulas, R³ and R⁴ each is a hydrogen atom or an alkyl,aryl or aralkyl group containing 1 to 20 carbon atoms and X is achlorine, bromine or iodine atom);

R³—C₆H₄—SO₂X

(in the above formula, R³ is a hydrogen atom or an alkyl, aryl oraralkyl group containing 1 to 20 carbon atoms and X is a chlorine,bromine or iodine atom); and the like.

An organic halide or halogenated sulfonyl compound having a furtherfunctional group in addition to the functional group for initiating thepolymerization may also be used as the initiator in atom transferradical polymerization. In such case, vinyl polymers having the furtherfunctional group at one main chain terminus and the structure of thegrowing terminus in atom transfer radical polymerization at the othermain chain terminus are produced. As such further functional group,there may be mentioned alkenyl, crosslinkable silyl, hydroxyl, epoxy,amino and amide groups, among others.

The alkenyl group-containing organic halide is not particularlyrestricted but includes, among others, those having a structurerepresented by the general formula 4:

R⁶R⁷C(X)—R⁸—R⁹—C(R⁵)═CH₂  (4)

wherein R⁵ is a hydrogen atom or a methyl group, R⁶ and R⁷ each is ahydrogen atom or a univalent alkyl, aryl or aralkyl group containing 1to 20 carbon atoms and such R⁶ and R⁷ groups may be bonded together atthe respective other ends, R⁸ is —C(O)O— (ester group), —C(O)— (ketogroup) or an o-, m- or p-phenylene group, R⁹ is a direct bond or abivalent organic group containing 1 to 20 carbon atoms, which maycontain one or more ether bonds, and X is a chlorine, bromine or iodineatom.

As specific examples of the substituent R⁶ and R⁷, there may bementioned a hydrogen atom, and methyl, ethyl, n-propyl, isopropyl,butyl, pentyl, hexyl and like groups. R⁶ and R⁷ may be connected to eachother at the respective other ends to form a cyclic skeleton.

As specific examples of the alkenyl-containing organic haliderepresented by the general formula 4, there may be mentioned thefollowing:

XCH₂C(O)O(CH₂)_(n)CH═CH₂, H₃CC(H)(X)C(O)O(CH₂)_(n)CH═CH₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)CH═CH₂, CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)CH═CH₂,

(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,

(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20);o-, m-, p-XCH₂—C₆H₄—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);o-, m-, p-XCH₂—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20);o-, m-, -p-XCH₂—C₆H₄—O—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20); ando-, m-, p-XCH₂—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20).

As the alkenyl-containing organic halide, there may further be mentionedcompounds represented by the general formula 5:

H₂C═C(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (5)

(wherein R⁵, R⁶, R⁷, R⁹ and X are the same as defined above and R¹⁰represents a direct bond, —C(O)O— (ester group), —C(O)— (keto group) oran o-, m- or p-phenylene group).

R⁸ is a direct bond or a divalent organic group (which may contain oneor more ether bonds) containing 1 to 20 carbon atoms. When it is adirect bond, a vinyl group is bound to the carbon atom to which ahalogen is bound, whereby an allyl halide compound is formed. In thiscase, the carbon-halogen bond is activated by the neighboring vinylgroup, so that R¹⁰ is not always required to be a C(O)O or phenylenegroup, for instance, but may be a direct bond. When R⁹ is other than adirect bond, R¹⁰ should preferably be a C(O)O, C(O) or phenylene groupso that the carbon-halogen bond may be activated.

Specific examples of the compound of general formula 5 are as follows:

CH₂═CHCH₂X, CH₂═C(CH₃)CH₂X, CH₂═CHC(H)(X)CH₃, CH₂═C(CH₃)C(H)(X)CH₃,CH₂═CHC(X)(CH₃)₂, CH₂═CHC(H)(X)C₂H₅,

CH₂═CHC(H)(X)CH(CH₃)₂, CH₂═CHC(H)(X)C₆H₅, CH₂═CHC(H)(X)CH₂C₆H₅,

CH₂═CHCH₂C(H)(X)—CO₂R, CH₂═CH₂(CH₂)₂C(H)(X)—CO₂R,CH₂═CH(CH₂)₃C(H)(X)—CO₂R, CH₂═CH(CH₂)₈C(H)(X)—CO₂R,CH₂═CHCH₂C(H)(X)—C₆H₅, CH₂═CH(CH₂)₂C(H)(X)—C₆H₅,CH₂═CH(CH₂)₃C(H)(X)—C₆H₅

(in the above formulas, X is a chlorine, bromine or iodine atom and R isan alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms), etc.

The following may be mentioned as specific examples of thealkenyl-containing halogenated sulfonyl compound:

o-, m-, p-CH₂═CH—(CH₂)_(n)—C₆H₄—SO₂X, o-, m-,p-CH₂═CH—(CH₂)_(n)—O—C₆H₄—SO₂X(in the above formulas, X is a chlorine, bromine or iodine atom and n isin integer of 0 to 20); etc.

The above-mentioned crosslinkable silyl-containing organic halide is notparticularly restricted but includes, among others, compounds having astructure represented by the general formula 6:

R⁶R⁷C(X)—R⁸—R⁹—C(H)(R⁵)CH₂—[Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (6)

(wherein R⁵, R⁶, R⁷, R⁸, R⁹ and X are the same as defined above, R¹¹ andR¹² each represents an alkyl, aryl or aralkyl group containing 1 to 20carbon atoms or a triorganosiloxy group represented by (R′)₃SiO— (inwhich R′ is a univalent hydrocarbon group containing 1 to 20 carbonatoms and the three R′ groups may be the same or different) and, whenthere are two or more R¹¹ or R¹² groups, they may be the same ordifferent; Y represents a hydroxyl group or a hydrolyzable group and,when there are two or more Y groups, they may be the same or different;a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m is an integerof 0 to 19 provided that the relation a+mb≧=1 is satisfied).

Specific examples of the compound of general formula 6 are as follows:

XCH₂C(O)O(CH₂)_(n)Si(OCH₃)₃, CH₃C(H)(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,(H₃C)₂C(X)C(O)O(CH₂)_(n)Si(OCH₃)₃, XCH₂C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,CH₃C(H)(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂(in the above formulas, X is a chlorine, bromine or iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20);o-, m-, p-XCH₂—C₆H₄—(CH₂)₂Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₃—Si(OCH₃)₃,o-, m-, p-XCH₂—C₆H₄—O—(CH₂)₂—O—(CH₂)₃—Si(OCH₃)₃,o-, m-, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,o-, m-, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃(in the above formulas, X is a chlorine, bromine or iodine atom); etc.

As further examples of the above-mentioned crosslinkablesilyl-containing organic halide, there may be mentioned compounds havinga structure represented by the general formula 7:

(R¹²)_(3-a)(Y)_(a)Si—[OSi(R¹¹)_(2-b)(Y)_(b)]_(m)—CH₂—C(H)(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (7)

wherein R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹¹, R¹², a, b, m, X and Y are the same asdefined above.

Specific examples of such compound are as follows:

(CH₃O)₃SiCH₂CH₂C(H)(X)C₆H₅, (CH₃O)₂(CH₃)SiCH₂CH₂C(H)(X)C₆H₅,(CH₃O)₃Si(CH₂)₂C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₂C(H)(X)—CO₂R,(CH₃O)₃Si(CH₂)₃C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—CO₂R,(CH₃O)₃Si(C₂)₄C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—CO₂R,(CH₃O)₃Si(CH₂)₉C(H)(X)—CO₂R, (CH₃O)₂(CH₃)Si(CH₂)₉C(H)(X)—CO₂R,(CH₃O)₃Si(CH₂)₃C(H)(X)—C₆H₅, (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—C₆H₅,(CH₃O)₃Si(CH₂)₄C(H)(X)—C₆H₅, (CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—C₆H₅

(in the above formulas, X is a chlorine, bromine or iodine atom and R isan alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms); etc.

The above-mentioned hydroxyl-containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, forexample, the following:

HO—(CH₂)_(n)—OC(O)C(H)(R)(X)wherein X is a chlorine, bromine or iodine atom, R is a hydrogen atom oran alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms and n isan integer of 1 to 20.

The above-mentioned amino-containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, forexample, the following:

H₂N—(CH₂)_(n)—OC(O)C(H)(R)(X)wherein X is a chlorine, bromine or iodine atom, R is a hydrogen atom oran alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms and n isan integer of 1 to 20.

The above-mentioned epoxy-containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, forexample, the following:

(wherein X is a chlorine, bromine or iodine atom, R is a hydrogen atomor an alkyl, aryl or aralkyl group containing 1 to 20 carbon atoms and nis an integer of 1 to 20).

For obtaining polymers having two or more growing terminal structuresspecified by the present invention in each molecule, an organic halideor halogenated sulfonyl compound having two or more initiation sites ispreferably used as the initiator. As specific examples, there may bementioned the following:

(in the above formulas, C₆H₄ is a phenylene group and X is a chlorine,bromine or iodine atom);

(in the above formulas, R is an alkyl, aryl or aralkyl group containing1 to 20 carbon atoms, n is an integer of 0 to 20 and X is a chlorine,bromine or iodine atom);

(in the above formulas, X is a chlorine, bromine or iodine atom and n isan integer of 0 to 20);

(in the above formulas, n is an integer of 1 to 20 and X is a chlorine,bromine or iodine atom);

(in the above formulas, X is a chlorine, bromine or iodine atom); etc.

The vinyl monomers to be used in this polymerization are notparticularly restricted but all those monomers mentioned herein above asexamples can appropriately be used.

The transition metal complex to be used as the catalyst is notparticularly restricted but preferably is a metal complex containing, asthe central atom, an element of the group 7, 8, 9, 10 or 11 of theperiodic table. More preferred are complexes of zero-valent copper,univalent copper, bivalent ruthenium, bivalent iron or bivalent nickel.Copper complexes are preferred among others. Specific examples of theunivalent copper compound are cuprous chloride, cuprous bromide, cuprousiodide, cuprous cyanide, cuprous oxide and cuprous perchlorate. Whensuch a copper compound is used, a ligand such as 2,2′-bipyridyl or aderivative thereof, 1,10-phenanthroline or a derivative thereof or apolyamine such as tetramethylethylenediamine,pentamethyldiethylenetriamine or hexamethyltris(2-aminoethyl)amine isadded for increasing the catalytic activity. Preferred ligands arenitrogen-containing compounds, more preferred ligands are chelate typenitrogen-containing compound, and still more preferred ligands areN,N,N′,N″,N″-pentamethyldiethylenetriamine. The tristriphenylphosphinecomplex of divalent ruthenium chloride (RuCl₂(PPh₃)₃) is also suited foruse as the catalyst. When such a ruthenium compound is used as thecatalyst, an aluminum alkoxide is added as an activator. Furthermore,the divalent iron-bistriphenylphosphine complex (FeCl₂(PPh₃)₂), thedivalent nickel-bistriphenylphosphine complex (NiCl₂(PPh₃)₂), and thedivalent nickel-bistributylphosphine complex (NiBr₂(PBu₃)₂) are alsosuited for use as the catalyst.

The polymerization can be carried out without using any solvent or inthe presence of various solvents. As the solvent species, there may bementioned hydrocarbon solvents such as benzene and toluene, ethersolvents such as diethyl ether and tetra hydrofuran, halogenatedhydrocarbon solvents such as methylene chloride and chloroform, ketonesolvents such as acetone, methyl ethyl ketone and methyl isobutylketone, alcohol solvents such as methanol, ethanol, propanol,isopropanol, n-butyl alcohol and tert-butyl alcohol, nitrile solventssuch as acetonitrile, propionitrile and benzonitrile, ester solventssuch as ethyl acetate and butyl acetate, carbonate solvents such asethylene carbonate and propylene carbonate, and the like. These may beused singly or two or more of them may be used in admixture.

The polymerization can be carried out within the temperature range of 0°C. to 200° C., preferably 50 to 150° C., although the temperature rangeis not limited to such range.

In the practice of the present invention, the atom transfer radicalpolymerization also includes the so-called reverse atom transfer radicalpolymerization. The reverse atom transfer radical polymerization is amethod comprising reacting an ordinary atom transfer radicalpolymerization catalyst in its high oxidation state resulting fromradical generation, for example Cu(II) when Cu(I) is used as thecatalyst, with an ordinary radical initiator, such as a peroxide, tothereby bring about an equilibrium state like in atom transfer radicalpolymerization (cf. Macromolecules, 1999, 32, 2872).

<Functional Groups>

The crosslinkable functional group in the vinyl polymer (II) is notrestricted. Preferred as such are, however, crosslinkable silyl groups,alkenyl groups, a hydroxyl group, an amino group, polymerizablecarbon-carbon double bond-containing groups, epoxy groups and likegroups.

These crosslinkable functional groups all can be used so as to adapt toor answer the intended use/purpose.

Positions of Crosslinkable Functional Groups

When the cured products derived from the curable composition of thepresent invention are required to have rubber-like properties, it isessential that at least one of the crosslinkable functional groupsconsist in at a molecular chain terminus in order that the molecularweight between crosslinking sites, which greatly influences on therubber elasticity, may be designed to be high. More preferably, allcrosslinkable functional groups should be located at molecular chaintermini.

Methods of producing such vinyl polymers, in particular (meth)acrylicpolymers, having at least one crosslinkable functional group aredisclosed in Japanese Kokoku Publication Hei-03-14068, Japanese KokokuPublication Hei-04-55444 and Japanese Kokai Publication Hei-06-211922,among others. However, these methods consist in the above-mentioned freeradical polymerization using a “chain transfer agent”, so that thepolymers obtained generally have a value of molecular weightdistribution represented by Mw/Mn as high as 2 or more, hence have aproblem in that their viscosity becomes high, although they have acrosslinkable functional group or groups at a molecular terminus ortermini with a relatively high percentage. Therefore, for obtaining avinyl polymer narrow in molecular weight distribution, low in viscosityand high in percentage of crosslinkable functional groups at molecularchain termini, the use of the above-mentioned “living radicalpolymerization technique” is preferred.

Number of Crosslinkable Functional Groups

The vinyl polymer (II) has at least one crosslinkable function group onaverage. From the composition curability viewpoint, the number of suchgroups is preferably more than 1, more preferably 1.1 to 4.0 on average,still more preferably 1.5 to 2.5.

In the following, an explanation is made of these functional groups.

Crosslinkable Silyl Groups

As the crosslinkable silyl groups to be used in the practice of thepresent invention, there may be mentioned those groups represented bythe general formula 8:

—[Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (8)

wherein, R¹¹ and R¹² each is an alkyl group containing 1 to 20 carbonatoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl groupcontaining 7 to 20 carbon atoms or a triorganosiloxy group representedby (R′)₃SiO— (in which R′ is a univalent hydrocarbon group containing 1to 20 carbon atoms and the three R′ groups may be the same or different)and, when there are two or more R¹¹ or R¹² groups, they may be the sameor different; Y represents a hydroxyl group or a hydrolyzable group and,when there are two or more Y groups, they may be the same or different;a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m is an integerof 0 to 19, provided that the relation a+mb≧1 should be satisfied.

As the hydrolyzable group, there may be mentioned, among others, ahydrogen atom and those groups which are in general use, for examplealkoxy, acyloxy, ketoximate, amino, amido, aminoxy, mercapto andalkenyloxy groups. Among them, alkoxy, amido and aminoxy groups arepreferred. In view of mild hydrolyzability and ease of handling, alkoxygroups are particularly preferred.

One to three hydroxyl groups and/or hydrolyzable groups can be bound toeach silicon atom and, in the practice of the present invention, it ispreferred that (a+Σb) be within the range of 1 to 5. When there are twoor more hydrolyzable groups or hydroxyl groups in one crosslinkablesilyl group, they may be the same or different. The number of siliconatoms forming the crosslinkable silyl group is not less than 1 and, inthe case of silicon atoms connected by siloxane or like bonding, it ispreferably not more than 20. Particularly preferred are crosslinkablesilyl groups represented by the general formula 9:

—Si(R¹²)_(3-a)(Y)_(a)  (9)

wherein R¹², Y and a are the same as defined above, because of readyavailability.

Those in which a is 3 (e.g. trimethoxy functional groups) are more rapidin curability than those in which a is 2 (e.g. dimethoxy functionalgroups) but may have problems with their storage stability or mechanicalproperties (elongation etc. in some instances. For attaining a balancebetween curability and physical properties, one in which a is 2 (e.g.dimethoxy functional groups) and one in which a is 3 (e.g. trimethoxyfunctional groups) may be used in combination.

Alkenyl Groups

The alkenyl group to be used in the practice of the invention is notparticularly restricted but preferably is one represented by the generalformula 10:

H₂C═C(R¹³)—  (10)

wherein R¹³ is a hydrogen atom or a hydrocarbon group containing 1 to 20carbon atoms.

In the general formula 10, R¹³ is a hydrogen atom or a hydrocarbon groupcontaining 1 to 20 carbon atoms, typical examples of which are thefollowing:

—(CH₂)_(n)—CH₃, —CH(CH₃)—(CH₂)_(n)—CH₃, —CH(CH₂CH₃)—(CH₂)_(n)—CH₃,—CH(CH₂CH₃)₂, —C(CH₃)₂—(CH₂)_(n)—CH₃, —C(CH₃)(CH₂CH₃)—(CH₂)_(n)—CH₃,—C₆H₅, —C₆H₅(CH₃), —C₆H₅(CH₃)₂, —(CH₂)_(n)—C₆H₅, —(CH₂)_(n)—C₆H₅(CH₃),—(CH₂)_(n)—C₆H₅(CH₃)₂(n being an integer of not less than 0 and the total number of carbonatoms in each group being not more than 20).

Among these, a hydrogen atom is preferred.

It is preferred, though not obligatory, that the alkenyl group(s) in thepolymer (II) be not activated by a carbonyl or alkenyl group or anaromatic ring, which is conjugated with the carbon-carbon double bond ofthe alkenyl group.

The mode of bonding of the alkenyl group to the polymer main chain isnot particularly restricted but preferably involves a carbon-carbonbond, ester bond, ether bond, carbonate bond, amide bond, or urethanebond, for instance.

Amino Groups

In the practice of the invention, the amino group is not particularlyrestricted but includes groups represented by

—NR¹⁴ ₂

wherein R¹⁴ is a hydrogen atom or an organic group containing 1 to 20carbon atoms and the two R¹⁴ groups may be the same or different or maybe bonded together at the respective other ends to form a ringstructure. It may be an ammonium salt represented by

—(NR¹⁴ ₃)⁺X⁻

wherein R¹⁴ is as defined above and X⁻ is a counter anion, without anyproblem.

In the above formulas, R¹⁴ is a hydrogen atom or a univalent organicgroup containing 1 to 20 carbon atoms and includes, among others, ahydrogen atom, alkyl groups containing 1 to 20 carbon atoms, aryl groupscontaining 6 to 20 carbon atoms, and aralkyl groups containing 7 to 20carbon atoms. The two R¹⁴ groups may be the same or different, or may bebonded together at the respective other ends to form a ring structure.

Groups Having a Polymerizable Carbon-Carbon Double Bond

The polymerizable carbon-carbon double bond-containing group ispreferably a group represented by the general formula 11:

—OC(O)C(R¹⁵)═CH₂  (11)

wherein R¹⁵ represents a hydrogen atom or a univalent organic groupcontaining 1 to 20 carbon atoms, more preferably a group of formula (11)in which R¹⁵ is a hydrogen atom or a methyl group.

Specific examples of R¹⁵ in general formula 11 include, but are notparticularly limited to, —H, —CH₃, —CH₂CH₃, —(CH₂)_(n)CH₃ (n being aninteger of 2 to 19), —C₆H₅, —CH₂OH, —CN and the like. Preferred are —Hand —CH₃, however.

<Functional Group Introduction Method>

In the following, several methods of functional group introduction intothe vinyl polymer (II) of the present invention are described, withoutany purpose of restriction, however.

First, methods of crosslinkable silyl, alkenyl or hydroxyl groupintroduction by terminal functional group conversion are described.These functional groups each can serve as a precursor of another and,therefore, mention is made in the order from crosslinkable silyl groupsto respective precursors.

As methods of synthesizing vinyl polymers having at least onecrosslinkable silyl group, there may be mentioned, among others, thefollowing.

(A) Method which comprises causing a crosslinkable silylgroup-containing hydrosilane compound to add to a vinyl polymer havingat least one alkenyl group in the presence of a hydrosilylationcatalyst;(B) Method which comprises reacting a vinyl polymer having at least onehydroxyl group with a compound having, in each molecule, a crosslinkablesilyl group and a group capable of reacting with the hydroxyl group,such as an isocyanato group;(C) Method which comprises subjecting a compound having, in eachmolecule, a polymerizable alkenyl group and a crosslinkable silyl groupto reaction in synthesizing a vinyl polymer by radical polymerization;(D) Method which comprises using a crosslinkable silyl group-containingchain transfer agent in synthesizing a vinyl polymer by radicalpolymerization; and(E) Method which comprises reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with a compound having, in eachmolecule, a crosslinkable silyl group and a stable carbanion.

The vinyl polymer having at least one alkenyl group, which is to be usedin the above method (A), can be obtained by various methods. Severalmethods of synthesis are mentioned below, without any purpose ofrestriction, however.

(A-a) Method comprising subjecting to reaction a compound having, ineach molecule, a polymerizable alkenyl group together with a lowpolymerizability alkenyl group, such as one represented by the generalformula 12 shown below, as a second monomer in synthesizing a vinylpolymer by radical polymerization:

—H₂C═C(R¹⁶)—R¹⁷—R¹⁸—C(R¹⁹)═CH₂  (12)

wherein R¹⁶ represents a hydrogen atom or a methyl group, R¹⁷ represents—C(O)O— or an o-, m- or p-phenylene group, R¹⁸ represents a direct bondor a bivalent organic group containing 1 to 20 carbon atoms, which maycontain one or more ether bonds, and R¹⁹ represents a hydrogen atom, analkyl group containing 1 to 20 carbon atoms, an aryl group containing 6to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms.

The time when the compound having, in each molecule, a polymerizablealkenyl group and a low polymerizability alkenyl group is subjected toreaction is not particularly restricted but, in particular in livingradical polymerization and when rubber-like properties are expected, thecompound is preferably subjected to reaction as a second monomer at thefinal stage of the polymerization reaction or after completion of thereaction of the monomer(s) employed.

(A-b) Method comprising subjecting to reaction a compound having atleast two low polymerizability alkenyl groups, for example1,5-hexadiene, 1,7-octadiene or 1,9-decadiene, at the final stage of thepolymerization or after completion of the reaction of the monomer(s)employed in vinyl polymer synthesis by living radical polymerization.

(A-c) Method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with one of variousalkenyl-containing organometallic compounds, for example an organotinsuch as allyltributyltin or allyltrioctyltin, for substitution for thehalogen.

(A-d) Method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with a stabilized,alkenyl-containing carbanion, such as one represented by the generalformula 13, for substitution for the halogen:

M⁺C⁻(R²⁰)(R²¹)—R²²—C(R¹⁹)═CH₂  (13)

wherein R¹⁹ is as defined above, R²⁰ and R²¹ each is anelectron-withdrawing group capable of stabilizing the carbanion C⁻ orone of them is such an electron-withdrawing group and the otherrepresents a hydrogen atom, an alkyl group containing 1 to 10 carbonatoms or a phenyl group, R²² represents a direct bond or a bivalentorganic group containing 1 to 10 carbon atoms, which may contain one ormore ether bonds, and M⁺ represents an alkali metal ion or a quaternaryammonium ion.

Particularly preferred as the electron-withdrawing group R²⁰ and/or R²¹are those which have a structure of —CO₂R, —C(O)R or —CN.

(A-e) Method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with a simple substance metal, suchas zinc, or an organometallic compound and then reacting thethus-prepared enolate anion with an alkenyl-containing, electrophiliccompound, such as an alkenyl-containing compound having a leaving groupsuch as a halogen atom or an acetyl group, an alkenyl-containingcarbonyl compound, an alkenyl-containing isocyanate compound or analkenyl-containing acid halide.

(A-f) Method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with an alkenyl-containing oxy anionor carboxylate anion, such as one represented by the general formula(14) or (15), for substitution for the halogen:

H₂C═C(R¹⁹)—R²³—O⁻M⁺  (14)

wherein R¹⁹ and M⁺ are the same as defined above and R²³ is a bivalentorganic group containing 1 to 20 carbon atoms, which may contain one ormore ether bonds;

H₂C═C(R¹⁹)—R²⁴—C(O)O⁻M⁺  (15)

wherein R¹⁹ and M⁺ are the same as defined above and R²⁴ is a directbond or a divalent organic group containing 1 to 20 carbon atoms, whichmay contain one or more ether bonds.

The method of synthesizing the above-mentioned vinyl polymer having atleast one highly reactive carbon-halogen bond includes, but is notlimited to, atom transfer radical polymerization techniques using anorganic halide or the like as initiator and a transition metal complexas catalyst, as mentioned above.

It is also possible to obtain the vinyl polymer having at least onealkenyl group from a vinyl polymer having at least one hydroxyl group.As utilizable methods, there may be mentioned, for example, thefollowing, without any purpose of restriction.

(A-g) Method comprising reacting the hydroxyl group(s) of a vinylpolymer having at least one hydroxyl group with a base, such as sodiummethoxide, followed by reaction with an alkenyl-containing halide, suchas allyl chloride.

(A-h) Method comprising reacting such hydroxyl group (s) with analkenyl-containing isocyanate compound, such as allyl isocyanate.

(A-i) Method comprising reacting such hydroxyl group(s) with analkenyl-containing acid halide, such as (meth)acrylic acid chloride, inthe presence of a base, such as pyridine.

(A-j) Method comprising reacting such hydroxyl group(s) with analkenyl-containing carboxylic acid, such as acrylic acid, in thepresence of an acid catalyst.

In the practice of the present invention, when no halogen is directlyassociated in the alkenyl group introduction, as in the method (A-a) or(A-b), the vinyl polymer is preferably synthesized by living radicalpolymerization. From the viewpoint of ready controllability, the method(A-b) is more preferred.

In cases where alkenyl group introduction is effected by conversion ofthe halogen atom(s) of a vinyl polymer having at least one highlyreactive carbon-halogen atom, use is preferably made of a vinyl polymerhaving at least one terminal carbon-halogen bond, which is highlyreactive, obtainable by subjecting a vinyl monomer(s) to radicalpolymerization (atom transfer radical polymerization) using, as aninitiator, an organic halide or halogenated sulfonyl compound having atleast one highly reactive carbon-halogen bond and, as a catalyst, atransition metal complex. In view of more ready controllability, themethod (A-f) is more preferred.

The crosslinkable silyl group-containing hydrosilane compound is notparticularly restricted but includes, as typical examples, compoundsrepresented by the general formula 16:

H—[Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (16)

wherein R¹¹ and R¹² each represents an alkyl group containing 1 to 20carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkylgroup containing 7 to 20 carbon atoms or a triorganosiloxy grouprepresented by (R′)₃SiO— (in which R′ is a univalent hydrocarbon groupcontaining 1 to 20 carbon atoms and the three R′ groups may be the sameor different) and, when there are two or more R¹¹ or R¹² groups, theymay be the same or different; Y represents a hydroxyl group or ahydrolyzable group and, when there are two or more Y groups, they may bethe same or different; a represents 0, 1, 2 or 3, b represents 0, 1 or 2and m is an integer of 0 to 19, provided that the relation a+mb≧1 shouldbe satisfied.

Particularly preferred among those hydrosilane compounds in view ofready availability are crosslinkable group-containing compoundsrepresented by the general formula 17:

H—Si(R¹²)_(3-a)(Y)_(a)  (17)

wherein R¹², Y and a are the same as defined above.

In causing the above crosslinkable silyl-containing hydrosilane compoundto add to the alkenyl group, a transition metal catalyst is generallyused. The transition metal catalyst includes, among others, simplesubstance platinum, solid platinum dispersed in/on a carrier such asalumina, silica or carbon black, chloroplatinic acid, chloroplatinicacid complexes with alcohols, aldehydes, ketones or the like,platinum-olefin complexes, and platinum(0)-divinyltetramethyldisiloxanecomplex. As other catalysts than platinum compounds, there may bementioned RhCl(PPh₃)₃, RhCl₃, RuCl₃, IrCl₃, FeCl₃, AlCl₃, PdCl₂.H₂O,NiCl₂ and TiCl₄, for instance.

The method of producing the Vinyl polymer having at least one hydroxylgroup, which polymer is to be used in the methods (B) and (A-g) to(A-j), includes, but is not limited to, the following, among others.

(B-a) Method comprising subjecting to reaction, as a second monomer, acompound having both a polymerizable alkenyl group and a hydroxyl groupin each molecule, for example one represented by the general formula 18given below, in synthesizing the vinyl polymer by radicalpolymerization:

H₂C═C(R¹⁶)—R¹⁷—R¹⁸—OH  (18)

wherein R¹⁶, R¹⁷ and R¹⁸ are the same as defined above.

The time for subjecting to reaction the compound having both apolymerizable alkenyl group and a hydroxyl group in each molecule is notcritical but, in particular in living radical polymerization, whenrubber-like properties are demanded, the compound is preferablysubjected to reaction as a second monomer at the final stage of thepolymerization reaction or after completion of the reaction of the mainmonomer(s).

(B-b) Method comprising subjecting an alkenyl alcohol, such as10-undecenol, 5-hexenol or allyl alcohol, to reaction at the final stageof polymerization reaction or after completion of the reaction of themain monomer(s) in synthesizing the vinyl polymer by living radicalpolymerization.

(B-c) Method comprising radical-polymerizing a vinyl monomer(s) using ahydroxyl-containing chain transfer agent, such as a hydroxyl-containingpolysulfide, in large amounts, as described in Japanese. KokaiPublication Hei-05-262808, for instance.

(B-d) Method comprising subjecting a vinyl monomer(s) to radicalpolymerization using hydrogen peroxide or a hydroxyl-containinginitiator, as described in/Japanese Kokai Publication Hei-06-239912 orJapanese Kokai Publication Hei-08-283310, for instance.

(B-e) Method comprising subjecting a vinyl monomer(s) to radicalpolymerization using an alcohol in excess, as described in JapaneseKokai Publication Hei-06-116312, for instance.

(B-f) Method comprising introducing a terminal hydroxyl group(s) byhydrolyzing the halogen atom(s) of a vinyl polymer having at least onehighly reactive carbon-halogen bond or reacting such halogen atom(s)with a hydroxyl-containing compound, according to the method describedin Japanese. Kokai Publication Hei-04-132706, for instance.

(B-g) Method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with a hydroxyl-containingstabilized carbanion, such as one represented by the general formula 19,for substitution for the halogen atom:

M⁺C⁻(R²⁰)(R²¹)—R²²—OH  (19)

wherein R²⁰, R²¹ and R²² are the same as defined above.

Particularly preferred as the electron-withdrawing groups R²⁰ and R²¹are those having a structure of —CO₂R, —C(O)R or —CN.

(B-h) Method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with a simple substance metal, suchas zinc, or an organometallic compound and then reacting thethus-prepared enolate anion with an aldehyde or ketone.

(B-i) Method comprising reacting a vinyl polymer having at least onehighly reactive carbon-halogen bond with a hydroxyl-containing oxy anionor carboxylate anion, such as one represented by the general formula 20or 21 given below, for substitution for the halogen atom:

HO—R²³—O⁻M⁺  (20)

wherein R²³ and M⁺ are the same as defined above;

HO—R²⁴—C(O)O⁻M⁺  (21)

wherein R²⁴ and M⁺ are the same as defined above.

(B-j) Method comprising subjecting, as a second monomer, a compoundhaving a low polymerizability alkenyl group and a hydroxyl group in eachmolecule to reaction at the final stage of the polymerization reactionor after completion of the reaction of the main monomer(s) insynthesizing the vinyl polymer by living radical polymerization.

Such compound is not particularly restricted but may be a compoundrepresented by the general formula 22, for instance:

H₂C═C(R¹⁶)—(R²³)—OH  (22)

wherein R¹⁶ and R²³ are the same as defined above.

The compound represented by the above general formula 22 is notparticularly restricted but, in view of ready availability, alkenylalcohols such as 10-undecenol, 5-hexenol and allyl alcohol arepreferred.

In the practice of the present invention, when no halogen is directlyassociated in hydroxyl group introduction, as in the methods (B-a) to(B-e) and (B-j), the vinyl polymer is preferably synthesized by livingradical polymerization. The method (B-b) is more preferred because ofready controllability.

In cases where hydroxyl group introduction is effected by conversion ofthe halogen atom(s) of a vinyl polymer having at least one highlyreactive carbon-halogen bond, use is preferably made of a vinyl polymerhaving at least one terminal carbon-halogen bond, which is highlyreactive, as obtained by subjecting a vinyl monomer(s) to radicalpolymerization (atom transfer radical polymerization) using an organichalide or halogenated sulfonyl compound as an initiator and, as acatalyst, a transition metal complex. From the ready controllabilityviewpoint, the method (B-i) is more preferred.

As the compound having a crosslinkable silyl group and a group capableof reacting with a hydroxyl group, such as an isocyanato group, in eachmolecule, there may be mentioned, for example,γ-isocyanatopropyltrimethoxysilane,γ-isocyanatopropylmethyldimethoxysialne,γ-isocyanatopropyltriethoxysilane and the like. If necessary, any ofurethane formation reaction catalysts generally known in the art can beused.

The compound having both a polymerizable alkenyl group and acrosslinkable silyl group in each molecule, which is to be used in themethod (C), includes, among others, trimethoxysilylpropyl(meth)acrylate, methyldimethoxysilylpropyl (meth)acrylate and likecompounds represented by the general formula 23:

H₂C═C(R¹⁶)—R¹⁷—R²⁵—[Si(R¹¹)]_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (23)

wherein R¹¹, R¹², R¹⁶, R¹⁷, Y, a, b and m are the same as defined aboveand R²⁵ is a direct bond or a bivalent organic group containing 1 to 20carbon atoms, which may contain one or more ether bonds.

The time for subjecting the compound having both a polymerizable alkenylgroup and a crosslinkable silyl group in each molecule is not criticalbut, in living radical polymerizationm in particular, and whenrubber-like properties are demanded, the compound is preferablysubjected to reaction as a second monomer at the final stage of thepolymerization reaction or after completion of the reaction of the mainmonomer(s).

As the crosslinkable silyl-containing chain transfer agent to be used inthe chain transfer agent method (D), there may be mentionedcrosslinkable silyl-containing mercaptans and crosslinkablesilyl-containing hydrosilanes, as described in Japanese KokokuPublication Hei-03-14068 and Japanese Kokoku Publication Hei-04-55444,among others.

The method of synthesizing the vinyl polymer having at least one highlyreactive carbon-halogen bond, which is to be used in the method (E),includes, but is not limited to, the atom transfer radicalpolymerization method which uses an organic halide or the like as aninitiator and a transition metal complex as a catalyst. As the compoundhaving both a crosslinkable silyl group and a stabilized carbanion ineach molecule, there may be mentioned compounds represented by thegeneral formula 24:

M⁺C⁻(R²⁰)(R²¹)—R²⁶—C(H)(R²⁷)—CH₂—[Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (24)

wherein R¹¹, R¹², R²⁰, R²¹, Y, a, b and m are the same as defined above,R²⁶ is a direct bond or a bivalent organic group containing 1 to 10carbon atoms, which may contain one or more ether bonds, and R²⁷represents a hydrogen atom, an alkyl group containing 1 to 10 carbonatoms, an aryl group containing 6 to 10 carbon atoms or an aralkyl groupcontaining 7 to 10 carbon atoms.

Particularly preferred as the electron-withdrawing groups R²⁰ and R²¹are those having a structure of —CO₂R, —C(O)R or —CN.

Epoxy Group

In the practice of the present invention, the vinyl polymer having aterminal reactive functional group(s) is produced by the followingsteps, though mentioning thereof has no restrictive meaning:

(1) producing a vinyl polymer by polymerizing a vinyl monomer(s) byliving radical polymerization; and then(2) reacting the polymer with a compound having a reactive functionalgroup and an ethylenically unsaturated group.

Mention may also be made of the method comprising subjecting allylalcohol to reaction at the final stage of atom transfer radicalpolymerization and then causing epoxy ring formation from the hydroxyland halogen groups.

Amino Group

The method of producing the vinyl polymer having at least one main chainterminal amino group may comprise the following steps:

(1) producing a vinyl polymer having at least one main chain terminalhalogen group; and(2) converting the terminal halogen group to an amino-containingsubstituent using an amino-containing compound.

The amino-containing substituent is not particularly restricted butincludes, for example, groups represented by the general formula 25:

—O—R²⁸—NR¹⁴ ₂  (25)

wherein R²⁸ represents a bivalent organic group containing 1 to 20carbon atoms, which may contain one or more ether or ester bonds; R¹⁴represents a hydrogen atom or a univalent organic group containing 1 to20 carbon atoms and the two R¹⁴ groups may be the same or different ormay be bonded together at the respective other ends to form a ringstructure.

In the above general formula 25, R²⁸ is a bivalent organic groupcontaining 1 to 20 carbon atoms, which may contain one or more ether orester bonds, and includes, among others, alkylene groups containing 1 to20 carbon atoms, arylene groups containing 6 to 20 carbon atoms andaralkylene groups containing 7 to 20 carbons atoms and, preferably,groups represented by:

—C₆H₄—R²⁹—

wherein C₆H₄ represents a phenylene group and R²⁹ represents a directbond or a bivalent organic group containing 1 to 14 carbon atoms, whichmay contain one or more ether or ester bonds, or

—C(O)—R³⁰—

wherein R³⁰ represents a direct bond or a bivalent organic groupcontaining 1 to 19 carbon atoms, which may contain one or more ether orester bonds.

An amino group can be introduced into a polymer terminus by converting aterminal halogen of the vinyl polymer. The method of substitution is notparticularly restricted but, from the ready reaction controllabilityviewpoint, a nucleophilic substitution reaction using anamino-containing compound as a nucleophile agent is preferred. As suchnucleophile agent, there may be mentioned compounds having both ahydroxyl group and an amino group as represented by the general formula26:

HO—R²⁸—NR¹⁴ ₂  (26)

wherein R²⁸ represents ambivalent organic group containing 1 to 20carbon atoms, which may contain one or more ether or ester bonds; R¹⁴represents a hydrogen atom or a univalent organic group containing 1 to20 carbon atoms and the two R¹⁴ groups may be the same or different ormay be bonded together at the respective other ends to form a ringstructure.

In the above general formula 26, R²⁸ is a bivalent organic groupcontaining 1 to 20 carbon atoms, which may contain one or more ether orester bonds, and includes, for example, alkylene groups containing 1 to20 carbon atoms, arylene groups containing 6 to 20 carbons andaralkylene groups containing 7 to 20 carbon atoms. Among these compoundshaving both a hydroxyl group and an amino group, aminophenols of theabove general formula in which R²⁸ is represented by

—C₆H₄—R²⁹—

wherein C₆H₄ represents a phenylene group and R²⁹ represents a directbond or a bivalent organic group containing 1 to 14 carbon atoms, whichmay contain one or more ether or ester bonds; and amino acids of theabove formula in which R²⁸ is represented by

—C(O)—R³⁰—

wherein R³⁰ represents a direct bond or a bivalent organic groupcontaining 1 to 19 carbon atoms, which may contain one or more ether orester bonds, are preferred.

As specific compounds, there may be mentioned, among others,ethanolamine; o-, m- or p-aminophenol; o-, m- or p-NH₂—C₆H₄—CO₂H;glycine, alanine and aminobutanoic acid.

A compound having both an amino group and an oxy anion can be used asthe nucleophilic reagent. Such compound is not particularly restrictedbut includes, for example, compounds represented by the general formula27:

M⁺O⁻—R²⁸—NR¹⁴ ₂  (27)

wherein R²⁸ represents a bivalent organic group containing 1 to 20carbon atoms, which may contain one or more ether or ester bonds; R¹⁴represents a hydrogen atom or a univalent organic group containing 1 to20 carbon atoms and the two R¹⁴ groups may be the same or different ormay be bonded together at the respective other ends to form a ringstructure; and M⁺ represents an alkali metal ion or a quaternaryammonium ion.

In the above general formula 27, M⁺ is a counter cation to the oxy anionand represents an alkali metal ion or a quaternary ammonium ion. Thealkali metal ion includes the lithium ion, sodium ion, potassium ion,etc., and preferably is the sodium ion or potassium ion. The quaternaryammonium ion includes the tetramethylammonium ion, tetraethylammoniumion, trimethylbenzylammonium ion, trimethyldodecylammonium ion,tetrabutylammonium ion, dimethylpiperidinium ion, etc.

Among the above-mentioned compounds having both an amino group and anoxy anion, salts of aminophenols represented by the general formula 28given below or salts of amino acids represented by the general formula29 given below are preferred in view of ready controllability of thesubstitution reaction or their ready availability:

M⁺O⁻—C₆H₄—R²⁹—NR¹⁴ ₂  (28)

M⁺O⁻—C(O)—R³⁰—NR¹⁴ ₂  (29)

wherein C₆H₄ represents a phenylene group, R²⁹ represents a direct bondor a bivalent organic group containing 1 to 14 carbon atoms, which maycontain one or more ether or ester bonds; R³⁰ represents a direct bondor a bivalent organic group containing 1 to 19 carbon atoms, which maycontain one or more ether or ester bonds; R¹⁴ represents a hydrogen atomor a univalent organic group containing 1 to 20 carbon atoms and the twoR¹⁴ groups may be the same or different or may be bonded together at therespective other ends to form a ring structure; and M⁺ is as definedabove.

The oxy anion-containing compound represented by the general formula 27,28 or 29 can be obtained with ease by reacting a compound represented bythe general formula 26 with a basic compound.

Various compounds can be used as the basic compound. Examples are sodiummethoxide, potassium methoxide, lithium methoxide, sodium ethoxide,potassium ethoxide, lithium ethoxide, sodium tert-butoxide, potassiumtert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate,sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodiumhydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium,tert-butyllithium, lithiumdiisopropylamide, lithiumhexamethyldisilazide,and the like. The amount of the above base is not particularlyrestricted but generally is 0.5 to 5 equivalents, preferably 0.8 to 1.2equivalents, relative to the above precursor.

As the solvent to be used in reacting the above precursor with the abovebase, there may be mentioned, among others, hydrocarbon solvents such asbenzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chlorideand chloroform; ketone solvents such as acetone, methyl ethyl ketone andmethyl isobutyl ketone; alcohol solvents such as methanol, ethanol,propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrilesolvents such as acetonitrile, propionitrile and benzonitrile; estersolvents such as ethyl acetate and butyl acetate; carbonate solventssuch as ethylene carbonate and propylene carbonate; amide solvents suchas dimethylformamide and dimethylacetamide; and sulfoxide solvents suchas dimethyl sulfoxide. These may be used singly or two or more of themmay be used in admixture.

The oxy anion-containing compound in which M⁺ is a quaternary ammoniumion can be obtained by preparing the corresponding compound in which M⁺is an alkali metal ion and reacting the same with a quaternary ammoniumhalide. As example of the quaternary ammonium halide; there may bementioned tetramethylammonium halides, tetraethylammonium halides,trimethylbenzylammonium halides, trimethyldodecylammonium halides, andtetrabutylammonium halides.

Various solvents may be used for the substitution reaction of thepolymer terminal halogen. As examples, there may be mentionedhydrocarbon solvents such as benzene and toluene; ether solvents such asdiethyl ether and tetra hydrofuran; halogenated hydrocarbon solventssuch as methylene chloride and chloroform; ketone solvents such asacetone, methyl ethyl ketone and methyl isobutyl ketone; alcoholsolvents such as methanol, ethanol, propanol, isopropanol, n-butylalcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile,propionitrile and benzonitrile; ester solvents such as ethyl acetate andbutyl acetate; carbonate solvents such as ethylene carbonate andpropylene carbonate; amide solvents such as dimethylformamide anddimethylacetamide; and sulfoxide solvents such as dimethyl sulfoxide.These may be used singly or in the form of a mixture of two or more.

The reaction can be carried out at a temperature of 0 to 150° C. Theamount of the amino-containing compound is not particularly restrictedbut generally is 1 to 5 equivalents, preferably 1 to 1.2 equivalents,relative to the polymer terminal halogen.

A basic compound may be added to the reaction mixture for promoting thenucleophilic substitution reaction. As such basic compound, there may bementioned those already mentioned herein above as well as alkylaminessuch as trimethylamine; triethylamine and tributylamine; polyamines suchas tetramethylethylenediamine and pentamethyldiethylenetriamine;pyridine compounds such as pyridine and picoline, and so on.

In cases where the amino group in the amino-containing compound used inthe nucleophilic substitution reaction affects the nucleophilicsubstitution reaction, the amino group is preferably protected with anappropriate substituent. Such substituent includes, among others,benzyloxycarbonyl, t-butoxycarbonyl and 9-fluorenylmethoxycarbonylgroup.

Mention may further be made of the method comprising substituting ahalogen terminus of a vinyl polymer with an azido anion and thenreducing the same with LAH or the like.

Polymerizable Carbon-Carbon Double Bond-Containing Groups

The method of introducing a polymerizable carbon-carbon doublebond-containing group into a polymer to give the polymer (II) accordingto the invention is not particularly restricted but may be any of thefollowing:

(i) Method comprising substituting a compound having aradical-polymerizable carbon-carbon double bond for a halogen group of avinyl polymer. A specific method comprises reacting a vinyl polymerhaving a structure represented by the general formula 30:

—CR³¹R³²X  (30)

wherein R³¹ and R³² each represents a group bonded to an ethylenicallyunsaturated group of the vinyl monomer and X represents a chlorine,bromine or iodine atom, with a compound represented by the generalformula 31:

M⁺—OC(O)C(R¹⁵)═CH₂  (31)

wherein R¹⁵ represents a hydrogen atom or an organic group containing 1to 20 carbon atoms and M⁺ represents an alkali metal ion or a quaternaryammonium ion.(ii) Method comprising reacting a hydroxyl-containing vinyl polymer witha compound represented by the general formula 32:

XC(O)C(R¹⁵)═CH₂  (32)

wherein R¹⁵ represents a hydrogen atom or an organic group containing 1to 20 carbon atoms and X represents a chlorine or bromine atom or ahydroxyl group.(iii) Method comprising reacting a hydroxyl-containing vinyl polymerwith a diisocyanate compound and then reacting the residual isocyanatogroup with a compound represented by the general formula 33:

HO—R³³—OC(O)C(R¹⁵)═CH₂  (33)

wherein R¹⁵ represents a hydrogen atom or an organic group containing 1to 20 carbon atoms and R³³ represents a bivalent organic groupcontaining 2 to 20 carbon atoms.

In the following, these methods are described in detail.

The above method (i) is described.

(i) The method comprising reacting a vinyl polymer having a terminalstructure represented by the general formula 30:

—CR³¹R³²X  (30)

wherein R³¹ and R³² each represents a group bonded to an ethylenicallyunsaturated group of the vinyl monomer and X represents a chlorine,bromine or iodine atom, with a compound represented by the generalformula 31:

M⁺⁻OC(O)C(R¹⁵)═CH₂  (31)

wherein R¹⁵ represents a hydrogen atom or an organic group containing 1to 20 carbon atoms and M⁺ represents an alkali metal ion or a quaternaryammonium ion.

The vinyl polymer having a terminal structure represented by the generalformula 30 is produced by the method comprising polymerizing a vinylmonomer(s) using the above-described organic halide or halogenatedsulfonyl compound as an initiator and the transition metal complex as acatalyst, or by the method comprising polymerizing a vinyl monomer(s)using a halogen compound as a chain transfer agent, preferably by theformer method.

The compound represented by the general formula 31 is not particularlyrestricted but, as specific examples of R¹⁵, there may be mentioned —H,—CH₃, —CH₂CH₃, —(CH₂)_(n)CH₃ (n being an integer of 2 to 19), —C₆H₅,—CH₂OH, —CN and the like. Among them, —H and —CH₃ are preferred. M⁺ isthe counter cation to the oxy anion and M⁺ includes, as species thereof,alkali metal ions, specifically the lithium ion, sodium ion andpotassium ion, and quaternary ammonium ions. As the quaternary ammoniumions, there may be mentioned the tetramethylammonium ion,tetraethylammonium ion, tetrabenzylammonium ion,trimethyldodecylammonium ion, tetrabutylammonium ion anddimethylpiperidinium ion, etc. The sodium ion and potassium ion arepreferred, however. The oxy anion of general formula 31 is usedpreferably in an amount of 1 to 5 equivalents, more preferably 1.0 to1.2 equivalents, relative to the halogen group of general formula 30.The solvent to be used in carrying out this reaction is not particularlyrestricted but preferably is a polar solvent since the reaction is anucleophilic substitution reaction. Thus usable are tetra hydrofuran,dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide,dimethylacetamide, hexamethylphosphoric triamide, acetonitrile and thelike. The temperature for carrying out the reaction is not particularlyrestricted but, generally, the reaction is carried out at 0 to 150° C.,preferably at room temperature to 100° C. so that the polymerizableterminal group may be retained.

The above-mentioned method (ii) is described.

(ii) The method comprising reacting a hydroxyl-containing vinyl polymerwith a compound represented by the general formula 32:

XC(O)C(R¹⁵)═CH_(Z)  (32)

wherein R¹⁵ represents a hydrogen atom or an organic group containing 1to 20 carbon atoms and X represents a chlorine or bromine atom or ahydroxyl group.

The compound represented by the general formula 32 is not particularlyrestricted but, as specific examples of R¹⁵, there may be mentioned —H,—CH₃, —CH₂CH₃, —(CH₂)_(n)CH₃ (n being an integer of 2 to 19), —C₆H₅,—CH₂OH, —CN and the like. Among them, —H and —CH₃ are preferred.

The vinyl polymer having a hydroxyl group(s), preferably at a terminusor termini, is produced by the method comprising polymerizing a vinylmonomer(s) using the above-mentioned organic halide or halogenatedsulfonyl compound as an initiator and the transition metal complex as acatalyst, or by the method comprising polymerizing a vinyl monomer(s)using a hydroxyl-containing compound as a chain transfer agent,preferably by the former method. Such method of producinghydroxyl-containing vinyl polymers includes; but is not limited to, thefollowing:

(a) Method comprising subjecting a compound having both a polymerizablealkenyl group and a hydroxyl group in each molecule, which isrepresented by the general formula 34, for instance:

H₂C═C(R³⁴)—R³⁵—R³⁶—OH  (34)

(wherein R³⁴ is an organic group containing 1 to 20 carbon atoms butpreferably is a hydrogen atom or a methyl group, and may be the same ordifferent; R³⁵ represents —C(O)O— (ester group) or an o-, m- orp-phenylene group; R³⁶ represents a direct bond or a bivalent organicgroup containing 1 to 20 carbon atoms, which may contain one or moreether bonds; the compound being a (meth)acrylate compound when R³⁵ is anester group, or a styrenic compound when R³⁵ is a phenylene group), toreaction as a second monomer in synthesizing a vinyl polymer by livingradical polymerization.

The time for subjecting the compound having both a polymerizable alkenylgroup and a hydroxyl group in each molecule to reaction is not criticalbut, in particular when rubber-like properties are demanded, thecompound is preferably subjected to reaction as a second monomer at thefinal stage of the polymerization reaction or after completion of thereaction of the main monomer(s).

(b) Method comprising subjecting a compound having alow-polymerizability alkenyl group and a hydroxyl group in eachmolecular to reaction as a second monomer in synthesizing a vinylpolymer by living radical polymerization at the final stage of thepolymerization reaction or after completion of the reaction of the mainmonomer(s).

Such compound is not particularly restricted but includes, among others,compounds represented by the general formula 35:

H₂C═C(R³⁴)—R³⁷—OH  (35)

wherein R³⁴ is as defined above; and R³⁷ represents a bivalent organicgroup containing 1 to 20 carbon atoms, which may contain one or moreether bonds.

The compound represented by the general formula 35 is not particularlyrestricted but preferably includes alkenyl alcohols such as10-undecenol, 5-hexenol and ally alcohol because of their readyavailability.

(c) Method comprising introducing a terminal hydroxyl group(s) byhydrolyzing the halogen atom(s) of a vinyl polymer having at least onehighly reactive carbon-halogen bond or reacting such halogen atom(s)with a hydroxyl-containing compound, according to the method describedin Japanese Kokai Publication Hei-04-132706, for instance.

(d) Method involving halogen substitution which comprises reacting avinyl polymer having at least one carbon-halogen bond such as onerepresented by the general formula 30, as obtained by atom transferradical polymerization, with a hydroxyl-containing stabilized carbanionsuch as one represented by the general formula 36:

M⁺C⁻(R³⁸)(R³⁹)—R³⁷—OH  (36)

wherein R³⁷ is as defined above; and R³⁸ and R³⁹ each represents anelectron-withdrawing group capable of stabilizing the carbanion C⁻ orone of them represents such an electron-withdrawing group and the otherrepresents a hydrogen atom, an alkyl group containing 1 to 10 carbonatoms or a phenyl group. As the electron-withdrawing groups R³⁸ and R³⁹,there may be mentioned —CO₂R (ester group), —C(O)R (keto group),—CON(R₂) (amide group), —COSR (thioester group), —CN (nitrile group),—NO₂ (nitro group), etc. The substituent R is an alkyl group containing1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms oran aralkyl group containing 7 to 20 carbon atoms, preferably an alkylgroup containing 1 to 10 carbon atoms or a phenyl group. Particularlypreferred as R³⁸ and R³⁹ are —CO₂R, —C(O)R and —CN.

(e) Method comprising reacting a vinyl polymer obtain able by atomtransfer radical polymerization and having at least one carbon-halogenbond such as one represented by the general formula 30 with a simplesubstance metal, such as zinc, or an organometallic compound and thenreacting the thus-prepared enolate anion with an aldehyde or ketone.

(f) Method comprising reacting a vinyl polymer having at least onepolymer terminal halogen, preferably a halogen group represented by thegeneral formula 30, with a hydroxyl-containing oxy anion represented bythe general formula 37 shown below, for instance, or ahydroxyl-containing carboxylate anion represented by the general formula38, for instance, for substituting a hydroxyl-containing group for thehalogen:

HO—R³⁷—O⁻M⁺  (37)

wherein R³⁷ and M⁺ are the same as defined above;

HO—R³⁷—C(O)O⁻M⁺  (38)

wherein R³⁷ and M⁺ are the same as defined above.

In the practice of the invention, when no halogen is directly associatedin the hydroxyl group introduction as in the methods (a) and (b), themethod (b) is more preferred because of more ready controllability.

In cases where the hydroxyl group introduction is effected by conversionof the halogen of a vinyl polymer having at least one carbon-halogenbond, such as in the methods (c) to (f), the method (f) is morepreferred because of easier controllability.

The above method (iii) is now described.

(iii) The method comprising reacting a hydroxyl-containing vinyl polymerwith a diisocyanate compound and then reacting the residual isocyanatogroup with a compound represented by the general formula 39:

HO—R³³—OC(O)C(R¹⁵)═CH₂  (39)

wherein R¹⁵ represents a hydrogen atom or an organic group containing 1to 20 carbon atoms and R³³ represents a bivalent organic groupcontaining 2 to 20 carbon atoms.

The compound represented by the general formula 39 is not particularlyrestricted but, as specific examples of R¹⁵, there may be mentioned —H,—CH₃, —CH₂CH₃, —(CH₂)_(n)CH₃ (n being an integer of 2 to 19), —C₆H₅,—CH₂OH, —CN and the like. Among them, —H and —CH₃ are preferred. As atypical compound, there may be mentioned 2-hydroxypropyl methacrylate.

The terminal hydroxyl-containing vinyl polymer is the same as mentionedherein above.

The diisocyanate compound is not particularly restricted but may be anyof those known in the art, for example toluoylene diisocyanate,4,4′-diphenylmethanediisocyanate, hexamethyl diisocyanate, xylylenediisocyanate, metaxylylene diisocyanate, 1,5-naphthalenediisocyanate,hydrogenated diphenylmethanediisocyanate, hydrogenated toluoylenediisocyanate, hydrogenated xylylene diisocyanate,isophoronediisocyanate, and like isocyanate compounds. These may be usedsingly or two or more of them may be used in combination. These may alsobe used in the form of blocked isocyanates.

For making better use of the excellent weatherability, the use ofaromatic ring-free diisocyanate compounds such as hexamethylenediisocyanate and hydrogenated diphenylmethanediisocyanate is preferred.

<<Re: Compatibilizing Agent (III)>>

The compatibilizing agent, namely component (III), to be used accordingto the present invention is a component to be added to compatibilize thepolyether polymer (I) with the vinyl polymer (II) and is a copolymerproduced by copolymerization of a plurality of vinyl monomers.

Preferred as the compatibilizing agent (III) according to the presentinvention are vinyl copolymers obtain able by copolymerizing at leastone vinyl monomer among the monomers used in polymerizing the vinylpolymer (II) and another vinyl monomer. Such vinyl copolymers may berandom copolymers or block copolymers.

The vinyl monomer to be used in the polymerization of the vinyl polymer(II) is not particularly restricted but includes those mentioned hereinabove. For example, when the vinyl polymer (II) is a (meth)acrylicpolymer, (meth)acrylic monomers are preferred, acrylic monomers are morepreferred, and acrylic ester monomers having a hydrocarbon group in theester moiety are still more preferred.

On the other hand, the other vinyl monomer is not particularlyrestricted but includes vinyl monomers other than the monomer(s) used inthe polymerization of the vinyl polymer (II), and vinyl monomers havinga polyether structure. In particular, vinyl monomers having a polyetherstructure are preferred.

The above polyether structure is not particularly restricted butpreferably is one comprising the same repeating unit as the repeatingunit in the polyether polymer (I) so that the compatibility with thepolyether polymer (I) may be improved. For example, when the main chainof the polyether polymer (I) is essentially polypropylene oxide, it ispreferred that the above polyether structure be essentiallypolypropylene oxide. The number of oxyalkylene units in each polyetherstructure may greatly vary depending on the average number of polyetherstructures contained in each molecule but, generally, it is 2 to 20 and,preferably, 2 to 10 in view of ease of synthesis. Furthermore, theterminus of the polyether structure may be a hydroxyl group itself ormay be blocked with a lower alkyl group. From the compatibilityviewpoint, one blocked with a lower alkyl group is preferred.

The vinyl monomer having a polyether structure is not particularlyrestricted but includes various species, among which a monomer of thesame kind as the monomer constituting the vinyl polymer (II). Forexample, when the vinyl polymer (II) is a (meth)acrylic polymer, a(meth)acrylic monomer having a polyether structure is preferred.Preferred as such (meth)acrylic monomer having a polyether structure is(meth)acrylic esters having a polyether structure in the ester moietythereof. More preferred are acrylic acid esters having a polyetherstructure in the ester moiety thereof. For example, mention may be madeof acrylic acid-ethylene oxide adducts, acrylic acid-propylene oxideadducts, and the like.

The proportions, in the compatibilizing agent (III), of the same vinylmonomer as used in the polymerization of the vinyl polymer (II) and thevinyl monomer having a polyether structure may vary greatly depending onthe mixing ratio between the polyether polymer (I) and vinyl polymer(II) and/or to the polyether structure. Generally, either monomerpreferably accounts for 1 to 99%, more preferably 5% to 95%, of thetotal number of moles of the monomers constituting the compatibilizingagent (III). In the compatibilizing agent (III), the mole ratio of thesame monomer as used in the polymerization of the vinyl polymer (II) tothe vinyl monomer having a polyether structure is not particularlyrestricted but, generally, it is 1:100 to 100:1, preferably 1:20 to20:1, more preferably 1:10 to 10:1. When the content of the polyetherpolymer (I) is high, the mole ratio of the vinyl monomer having apolyether structure is preferably increased.

The number average molecular weight of the compatibilizing agent (III)according to the present invention is not particularly restricted butpreferably is within the range of 500 to 50,000, more preferably withinthe range of 1,000 to 10,000, which is determined by gel permeationchromatography. If the molecular weight is lower, the effect as acompatibilizing agent may not be expressed. When the molecular weight ishigher, the viscosity may become high, possibly causing handlingdifficulties.

The method of synthesizing the compatibilizing agent (III) according tothe present invention is not particularly restricted but may involvefree radical polymerization or controlled radical polymerization. Fromthe viewpoint of various characteristics of curable compositions obtainable, controlled radical polymerization is preferred, living radicalpolymerization is more preferred, and atom transfer radicalpolymerization is still more preferred.

<<Compatibilizing Agent (IV)>>

The component (IV) compatibilizing agent to be used according to theinvention is a component to be added for compatibilizing the polyetherpolymer (I) with the vinyl polymer (II) and comprises at least onecompound selected from the group consisting of nonpolymer organiccompounds, polymers obtain able by polymerizing a monomer(s) other thanvinyl monomers, and polymers obtain able by polymerizing a single vinylmonomer.

The nonpolymer organic compounds are not particularly restricted butinclude, among others, phthalates, such as dibutyl phthalate, diheptylphthalate, di(2-ethylhexyl) phthalate and butyl benzyl phthalate;nonaromatic dibasic acid esters such as dioctyl adipate, dioctylsebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters suchas butyl oleate and methyl acetylricirinoleate; polyalkylene glycolesters such as diethylene glycol dibenzoate, triethylene glycoldibenzoate and pentaerythritol esters; phosphates such as tricresylphosphate and tributyl phosphate; and trimellitates.

The polymers obtain able by polymerizing a monomer(s) other than vinylmonomers are not particularly restricted but include, among others,chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls andpartially hydrogenated terphenyl; process oils; polyether polyols such,as polyethylene glycol, polypropylene glycol and polytetramethyleneglycol, derivatives of these polyether polyols by conversion of thehydroxyl groups to ester or ether groups, and like polyethers; epoxyplasticizers such as epoxidized soybean oil and benzyl epoxystearate;and polyester plasticizers obtain able from dibasic acids such assebacic acid, adipic acid, azelaic acid and phthalic acid and dihydricalcohols such as ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol and dipropylene glycol.

The polymers obtain able by polymerizing a single vinyl monomer are notparticularly restricted but include, among others, polystyrenes such aspolystyrene and poly-α-methylstyrene; polybutadiene, polybutene,polyisobutylene, butadiene-acrylonitrile copolymers, polychloroprene;acrylic plasticizers, and like vinyl polymers obtain able bypolymerizing vinyl monomers by various methods.

The above-mentioned acrylic plasticizers are not particularly restrictedbut include, among others, conventional ones obtain able by solutionpolymerization and solventless acrylic polymers. The latter acrylicplasticizers are more suited for the purpose of the present inventionsince they are produced by high-temperature continuous polymerizationtechniques (U. S. Pat. No. 4,414,370, Japanese Kokai PublicationSho-59-6207, Japanese Kokoku Publication Hei-05-58005, Japanese KokaiPublication Hei-01-313522, U. S. Pat. No. 5,010,166), without using anysolvent or chain transfer agent. Examples thereof are not particularlyrestricted but include, among others, UP series products (Toagosei Co.,Ltd.) (cf. Kogyo Zairyo (Magazine for Engineering Materials), October1999 issue).

When the polymer obtain able by polymerizing a single vinyl monomer isused as the compatibilizing agent, the molecular weight thereof is notparticularly restricted but preferably is not more than 3,000 from thecompatibility viewpoint. The main chain thereof is not particularlyrestricted but preferably is a polyolefin. A polyoxyalkylene is alsopreferred, and polypropylene oxide is more preferred.

The content of the compatibilizing agent (IV) is preferably 1 to 200parts by weight, more preferably 5 to 150 parts by weight, mostpreferably 10 to 100 parts by weight, relative to 100 parts by weight ofthe sum of the polyether polymer (I), and vinyl polymer (II).

<<Curable Composition>>

In the curable composition of the present invention, a curing catalystand/or a curing agent may be required according to the curablefunctional group species. Any of various compounding additives oringredients may be added thereto according to the physical propertiesrequired.

<Curing Catalyst, Curing Agent> In the Case of Crosslinkable SilylGroups

The crosslinkable silyl group-containing polymer is crosslinked andcured under siloxane bond formation in the presence or absence ofvarious condensing catalysts known in the art. The properties of thecured products can widely range from rubber-like to resinous onesaccording to the molecular weight and main chain skeleton of thepolymer.

As examples of such condensing catalyst, there may be mentioned, amongothers, tetravalent tin compounds such as dibutyltin dilaurate,dibutyltin phthalate, dibutyltin bisacetylacetonate, dibutyltindiacetate, dibutyltin diethylhexanolate, dibutyltin dioctoate,dibutyltin di(methyl maleate), dibutyltin di(ethyl maleate), dibutyltindi(butyl maleate), dibutyltin di(isooctyl maleate), dibutyltindi(tridecyl maleate), dibutyltin di(benzyl maleate), dibutyltin maleate,dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate,dioctyltin di(ethyl maleate), dioctyltin di(isooctyl maleate),dibutyltin dimethoxide, dibutyltin bisnonylphenoxide and dibutenyltinoxide; divalent tin compounds such as stannous octylate, stannousnaphthenate and stannous stearate; titanate esters such as tetrabutyltitanate and tetrapropyl titanate; organoaluminum compounds such asaluminum trisacetylacetonate, aluminum tris(ethyl acetoacetate) anddiisopropoxyaluminum ethyl acetoacetate; chelate compounds such aszirconium tetraacetylacetonate and titanium tetraacetylacetoante; leadoctylate; amine compounds such as butylamine, octylamine, laurylamine,dibutylamine, monoethanolamine, diethanolamine, triethanolamine,diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine,2-ethyl-4-methylimidazole and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU),or salts of these amine compounds with carboxylic acids; aminecompound-organotin compound reaction products and mixtures, for examplelaurylamine-stannous octylate reaction products or mixtures;low-molecular-weight polyamide resins obtain able from a polyamine inexcess and a polybasic acid; reaction products from a polyamine inexcess and an epoxy compound; amino group-containing silane couplingagents such as γ-aminopropyltrimethoxysilane andN-(β-aminoethyl)aminopropylmethyldimethoxysilane; and like silanolcondensation catalysts and, further, other known silanol condensationcatalysts such as acidic catalysts and basic catalysts.

These catalysts may be used singly or two or more of them may be used incombination. The level of addition of such condensation catalyst ispreferably about 0.1 to 20 parts (by weight; herein after the same shallapply), more preferably 1 to 10 parts, per 100 parts of the vinylpolymer (II) having at least one crosslinkable silyl group. When theaddition level of the silanol condensing catalyst is below the aboverange, the rate of curing may fall and the curing can hardly proceed toa satisfactory extent in certain cases. Conversely, when the level ofaddition of the silanol condensation catalyst exceeds the above range,local heat generation and/or foaming may occur in the step of curing,making it difficult to obtain good cured products; in addition, the potlife becomes excessively short and this is unfavorable from theworkability viewpoint as well.

For further increasing the activity of the condensation catalyst in thecurable composition of the present invention, a silanol group-freesilicon compound represented by the general formula 40:

(R⁴⁹)_(a)Si(OR⁵⁰)_(4-a)  (40)

wherein R⁴⁹ and R⁵⁰ each independently is a substituted or unsubstitutedhydrocarbon group containing 1 to 20 carbon atoms and a is 0, 1, 2 or 3,may be added to the composition.

The above silicon compound is not restricted but those compounds of thegeneral formula (40) in which R⁴⁹ is an aryl group containing 6 to 20carbon atoms, such as phenyltrimethoxysilane,phenylmethyldimethoxysilane, phenyldimethylmethoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane andtriphenylmethoxysilane, are preferred since their accelerating effect onthe curing reaction of the composition is significant. In particular,diphenyldimethoxysilane and diphenyldiethoxysilane are low in cost andreadily available, hence are most preferred.

The level of addition of this silicon compound is preferably about 0.01to 20 parts, more preferably 0.1 to 10 parts, per 100 parts of the vinylpolymer (II) having at least one crosslinkable silyl group. When thelevel of addition of the silicon compound is below this range, thecuring reaction-accelerating effect may decrease in certain cases. When,conversely, the level of addition of the silicon compound exceeds thisrange, the hardness and/or tensile strength of the cured products mayfall.

In the Case of Alkenyl Groups

When alkenyl groups are associated in the crosslinking, it is preferredthough not obligatory, that the crosslinking be effected in the mannerof hydrosilylation using a hydrosilyl group-containing compound as acuring agent, together with a hydrosilylation catalyst.

The hydrosilyl group-containing compound is not particularly restrictedbut may be any of various hydrosilyl group-containing compounds whichcan cure with the alkenyl-containing polymer by crosslinking. Forexample, use may be made of linear polysiloxanes represented by thegeneral formula 41 or 42:

R⁵¹ ₃SiO—[Si(R⁵¹)₂O]_(a)—[Si(H)(R⁵²)O]_(b)—[Si(R⁵²)(R⁵³)O]_(c)—SiR⁵¹₃  (41)

HR⁵¹ ₂SiO—[Si(R⁵¹)₂O]_(a)—[Si(H)(R⁵²)O]_(b)—[Si(R⁵²)(R⁵³)O]_(c)—SiR⁵¹₂H  (42)

wherein R⁵¹ and R⁵² each represents an alkyl group containing 1 to 6carbon atoms or a phenyl group, R⁵³ represents an alkyl group or aralkylgroup containing 1 to 10 carbon atoms, and a, b and c each represents aninteger satisfying the relations 0≦a≦100, 2≦b≦100 or 0≦c≦100);cyclic siloxanes represented by the general formula 43:

wherein R⁵⁴ and R⁵⁵ each represents an alkyl group containing 1 to 6carbon atoms or a phenyl group, R⁵⁶ represents an alkyl group or aralkylgroup containing 1 to 10 carbon atoms, and d, e and f each represents aninteger satisfying the relations 0≦d≦8, 2≦e≦10 or 0≦f≦8 provided thatthe relation 3≦d+e+f≦10 should be satisfied; and like compounds.

These may be used singly or two or more of them may be used inadmixture. Among these siloxanes, phenyl-containing: linear siloxanesrepresented by the general formula 44 or 45 shown below and cyclicsiloxanes represented by the general formula 46 or 47 shown below arepreferred from the viewpoint of compatibility with the (meth)acrylicpolymers.

(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(C₆H₅)₂O]_(h)—Si(CH₃)₃  (44)

(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(CH₃{CH₂C(H)(R⁵⁷)C₆H₅}O)_(h)—Si(CH₃)₃  (45)

(In the above formulas, R⁵⁷ represents a hydrogen atom or a methylgroup, g and h each represents an integer satisfying the relation2≦g≦100 or 0≦h≦100, and C₆H₅ represents a phenyl group.)

(In the above formulas, R⁵⁷ represents a hydrogen atom or a methylgroup, i and j each represents an integer satisfying the relation 2≦i≦10or 0≦j≦8 provided that the relation 3≦i+j≦10 should be satisfied; andC₆H₅ represents a phenyl group.)

Further usable as the hydrosilyl-containing compound are compoundsobtain able by subjecting a low-molecular-weight compound having two ormore alkenyl groups in each molecule and a hydrosilyl-containingcompound represented by any of the general formulas 41 to 47 to additionreaction in a manner such that the hydrosilyl group partially remainseven after reaction. Usable as the compound having two or more alkenylgroups in the molecule are various compounds, for example hydrocarboncompounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene and 1,9-decadiene, ether compounds such asO,O′-diallylbisphenol A and 3,3′-diallylbisphenol A, ester compoundssuch as diallyl phthalate, diallyl isophthalate, triallyl trimellitateand tetraallyl pyromellitate, and carbonate compounds such as diethyleneglycol diallyl carbonate.

The above compounds can be obtained by slowly adding dropwise thealkenyl-containing compound to an excess of the hydrosilyl-containingcompound represented by one of the general formulas 41 to 47 shown abovein the presence of a hydrosilylation catalyst. Among such compounds, thefollowing ones are preferred in view of the readily availability of rawmaterials, the ease of removal of the siloxane used in excess and,further, the compatibility with the (I) component polymer:

(n being an integer of 2 to 4 and m being an integer of 0.5 to 10).

The polymer and curing agent may be mixed together in an arbitrary ratiobut, from the curability viewpoint, the mole ratio between the alkenyland hydrosilyl groups is preferably within the range of 5 to 0.2, morepreferably within the range of 2.5 to 0.4. When the mole ratio is above5, the curing becomes insufficient and only cured products havingsurface tack and low strength can be obtained. When it is lower than0.2, the active hydrosilyl group remains in large amounts in the curedproducts even after curing, so that cracks and voids appear and nouniform and strong cured products can be obtained.

The curing reaction between the polymer and curing agent proceeds whenthe two components are mixed up and heated. For causing the reaction toproceed more rapidly, a hydrosilylation catalyst may be added. Suchhydrosilylation catalyst is not particularly restricted but may be, forexample, a radical initiator such as an organic peroxide or azocompound, or a transition metal catalyst.

The radical initiator is not particularly restricted but includes, amongothers, dialkyl peroxides such as di-t-butyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide and α, α′-bis(t-butylperoxy)isopropylbenzene, diacylperoxides such as benzoyl peroxide, p-chlorobenzoyl peroxide,m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroylperoxide, peroxy esters such as t-butyl perbenzoate, peroxydicarbonatessuch as diisopropyl peroxydicarbonate and di-2-ethylhexylperoxydicarbonate, peroxy ketals such as1,1-di(t-butylperoxy)cyclohexane and1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, and the like.

The transition metal catalyst is not particularly restricted, either,but includes, among others, simple substance platinum, solid platinumdispersed on/in a carrier such as alumina, silica or carbon black,chloroplatinic acid, chloroplatinic acid complexes with alcohols,aldehydes, ketones or the like, platinum-olefin complexes, andplatinum(0)-divinyltetramethyldisiloxane complex. As other catalyststhan platinum compounds, there may be mentioned RhCl(PPh₃)₃, RhCl₃,RuCl₃, IrCl₃, FeCl₃, AlCl₃, PdCl₂.H₂O, NiCl₂ and TiCl₄, for instance.These catalysts may be used singly or two or more of them may be used incombination. The amount of the catalyst is not particularly restrictedbut recommendably is within the range of 10⁻¹ to 10⁻⁸ mole, preferably10⁻³ to 10⁻⁶ mole, per mole of the alkenyl group in the vinyl polymer(II). When it is less than 10⁻⁸ mole, the curing will not proceed to asufficient extent. Since the hydrosilylation catalyst is expensive, itis preferred that it be not used in an amount exceeding 10⁻¹ mole.

The curing temperature is not particularly restricted but,recommendably, the curing is carried out generally at 0° C. to 200° C.,preferably at 30° C. to 150° C., more preferably at 80° C. to 150° C.

In the Case of Hydroxyl Group

The hydroxyl-containing polymer according to the invention can be cureduniformly by using, as a curing agent, a compound having two or morefunctional groups capable of reacting with the hydroxyl group. Asspecific examples of the curing agent, there may be mentioned, amongothers, polyvalent isocyanate compounds having two or more isocyanatogroups in each molecule, aminoplast resins such as methylolated melamineand alkyl-etherification derivatives thereof or low condensationproducts thereof, and polufunctional carboxylic acids and halogenationderivatives thereof. When cured products are to be produced by usingthese curing agents, appropriate curing catalysts can be used for therespective curing agents.

In the Case of Amino Groups

The amino group-containing polymer according to the present inventioncan be cured uniformly by using, as a curing agent, a compound havingtwo or more functional groups capable of reacting with the aminogroup(s). As specific examples of the curing agent, there may bementioned, among others, polyvalent isocyanate compounds having two ormore isocyanato groups in each molecule, aminoplast resins such asmethylolated melamine and alkyl-etherification derivatives thereof orlow condensation products thereof, and polyfunctional carboxylic acidsand halogenation derivatives thereof. When cured products are to beproduced by using these curing agents, appropriate curing catalysts canbe used for the respective curing agents.

In the Case of Epoxy Group

The curing agent to be used for the epoxy-containing polymer accordingto the invention is not particularly restricted. Usable as such are, forexample, aliphatic amines, alicyclic amines, aromatic amines; acidanhydrides; polyamides; imidazoles; amineimides; urea; melamine andderivatives thereof; polyamine salts; phenol resins: polymercaptans,polysulfides; and photocuring/ultra violet curing agents such asaromatic diazonium salts, diallyliodonium salts, triallylsulfonium saltsand triallylselenium salts.

In the Case of Polymerizable Carbon-Carbon Double Bonds

The polymerizable carbon-carbon double bond-containing polymer can becrosslinked through the polymerization reaction of its polymerizablecarbon-carbon double bond(s).

The method of crosslinking includes curing with activating energy rays,and curing by means of heat. In the activating energy ray-curablecomposition, the photopolymerization initiator is preferably aphotoradical initiator or a photoanion initiator. In thermocurablecompositions, the heat polymerization initiator is preferably selectedfrom the group consisting of azo initiators, peroxides, persulfates, andredox initiator systems.

In the following, these crosslinking reactions are described in detail.

When the polymerizable carbon-carbon double bond-containing polymer isto be crosslinked, a polymerizable monomer and/or oligomer and/orvarious additives may be combinedly used according to the intendedpurpose. Preferred as the polymerizable monomer and/or oligomer aremonomers and/or oligomers having a radical-polymerizable group or ananionically polymerizable group. The radical-polymerizable groupincludes acrylic functional groups such as a (meth)acrylic group,styrene group, acrylonitrile group, vinyl ester group,N-vinylpyrrolidone group, acrylamide group, conjugated diene group,vinyl ketone group, vinyl chloride group, etc. Among them, those havinga (meth)acrylic group similar to the polymer of the invention arepreferred. The anionically polymerizable group includes a (meth)acrylicgroup, styrene group, acrylonitrile group, N-vinylpyrrolidone group,acrylamide group, conjugated diene group, vinyl ketone group, etc. Amongthem, those having an acrylic functional group are preferred.

As specific examples of the above monomer, there may be mentioned(meth)acrylate monomers, cyclic acrylates, N-vinylpyrrolidone, styrenicmonomers, acrylonitrile, N-vinylpyrrolidone, acrylamide monomers,conjugated diene monomers, vinyl ketone monomers, etc. As the(meth)acrylate monomers, there may be mentioned n-butyl (meth)acrylate2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl(meth)acrylate, and compounds of the following, formulas:

The styrenic monomers include styrene, α-methylstyrene, and the like,the acrylamide monomers include acrylamide, N,N-dimethylacrylamide, andthe like, the conjugated diene monomers include butadiene, isoprene, andthe like, and the vinyl ketone monomers include methyl vinyl ketone andthe like.

As the polyfunctional monomers, there may be mentioned neopentyl glycolpolypropoxy diacrylate, trimethylolpropane polyethoxy triacrylate,bisphenol F polyethoxy diacrylate, bisphenol A polyethoxy diacrylate,dipentaerythritol polyhexanolide hexaacrylate, tris(hydroxyethyl)isocyanurate polyhexanolide triacrylate, tricyclodecanedimethyloldiacrylate,2-(2-acryloyloxy-1,1-dimethyl)-5-ethyl-5-acryloyloxymethyl-1,3-dioxane,tetrabromobisphenol A diethoxy diacrylate, 4,4′-dimercaptodiphenylsulfide dimethacrylate, polytetraethylene glycol diacrylate,1,9-nonandiol diacrylate, ditrimethylolpropane tetraacrylate, etc.

As the oligomers, there may be mentioned bisphenol A-based epoxyacrylate resins, phenol novolak-based epoxy acrylate resins, cresolnovolak-based epoxy acrylate resins and like epoxy acrylate resins,COOH-modified epoxy acrylate resins, urethane acrylate resins obtainable by reacting urethane resins prepared from a polyol (e.g.polytetramethylene glycol, polyester diol derived from ethylene glycoland adipic acid, ε-caprolactone-modified polyester diol, polypropyleneglycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminatedhydrogenated polyisoprene, hydroxyl-terminated polybutadiene,hydroxyl-terminated polyisobutylene, etc.) and an organic isocyanate(e.g. tolylene diisocyanate, isophoronediisocyanate,diphenylmethanediisocyanate hexamethylene diisocyanate, xylylenediisocyanate) with a hydroxyl-containing (meth)acrylate (e.g.hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl(meth)acrylate, pentaerythritol triacrylate), resins derived from theabove-mentioned polyol by introduction of a (meth)acrylic group viaester bonding, polyester acrylate resins, and so forth.

An appropriate one is to be selected from among these monomers andoligomers according to the initiator and curing conditions employed.

It is preferred for good compatibility reasons that the acrylicfunctional group-containing monomer and/or oligomer have a numberaverage molecular weight of not higher than 2,000, more preferably nothigher than 1,000.

As for the method of crosslinking the polymerizable carbon-carbon doublebond-containing polymer, the use of UV or electron beams or likeactivating energy rays is preferred.

When crosslinking is to be accomplished by means of activating energyrays, it is preferred that the composition contain a photopolymerizationinitiator.

The photopolymerization initiator to be used in the practice of theinvention is not particularly restricted but preferably is aphotoradical initiator or photoanion initiator, in particular aphotoradical initiator. As examples, there may be mentionedacetophenone, propiophenone, benzophenone, xanthol, fluorein,benzaldehyde, anthraquinone, triphenylamine, carbazole,3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone,4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone,p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone,4-chlorobenzophenone, 4,4′-dimethoxybenzophenone,4-chloro-4′-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone,3-chloro-8-nonylxanthone, benzoil, benzoin methyl ether, benzoin butylether, bis(4-dimethylaminophenyl) ketone, benzyl methoxy ketal,2-chlorothioxanthone, and the like. These initiators may be used singlyor in combination with another compound. More specifically, mention maybe made of combinations with amines such as diethanol/methylamine,dimethylethanolamine and triethanolamine, optionally further combinedwith an iodonium salt such as diphenyliodonium chloride, andcombinations with a dye, such as Methylene Blue, and an amine.

Further, a near infrared-absorbing cationic dye may also be used as aneat infrared photopolymerization initiator. The near infrared-absorbingcationic dye to be used is preferably a near infrared-absorbing cationicdye-borate anion complex capable of being excited by light energy in theregion of 650 to 1,500 nm, such as one disclosed in Japanese KokaiPublication Hei-03-111402 or Japanese Kokai Publication Hei-05-194619,for instance. The combined use of a boron-containing sensitizer is morepreferred.

The level of addition of the photopolymerization initiator is such thatthe system can be photofunctionalized only slightly; hence it is notparticularly restricted. Preferably, however, the level is 0.001 to 10parts by weight per 100 parts of the polymer in the composition.

The method of curing the activating energy ray-curable composition ofthe present invention is not particularly restricted but may involveirradiation with light rays or electron beams using a high-pressuremercury lamp, low-pressure mercury lamp, electron beam irradiationequipment, halogen lamp, light emitting diode, semiconductor laser, etc.according to the characteristics of the photopolymerization initiator.

As for the method of crosslinking the polymerizable carbon-carbon doublebond-containing polymer, the use of heat is preferred.

In effecting the crosslinking by means of activating energy rays, it ispreferred that the composition contain a heat polymerization initiator.

The heat polymerization initiator to be used in the practice of thepresent invention is not particularly restricted but includes azoinitiators, peroxides, persulfate salts, and redox initiator systems.

Suitable azo initiators include, but are not limited to,2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33),2,2′-azobis(2-amidinopropane) dihydrochloride (VAZO 50),2,2′-azobis(2,4-dimethylvaleronitrile) (VAZO 52),2,2′-azobis(isobutyronitrile) (VAZO 64),2,2′-azobis-2-methylbutyronitrile (VAZO 67),1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88) (all available fromDuPont Chemical), 2,2′-azobis(2-cyclopropylpropionitrile), and2,2′-azobis(methyl isobutyrate) (V-601) (available from Wako PureChemical Industries), among others.

Appropriate peroxide initiators include, but are not limited to, benzoylperoxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetylperoxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (Perkadox16S) (available from Akzo Nobel), di(2-ethylhexyl) peroxydicarbonate,t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem),t-butyl peroxy-2-ethylhexanoate (Trigonox 21-C50) (available from AkzoNobel) and dicumyl peroxide, among others.

Appropriate persulfate initiators include, but are not limited to,potassium persulfate, sodium persulfate and ammonium persulfate, amongothers.

Suitable redox (oxidation/reduction) initiators include, but are notlimited to, combinations of the above-mentioned persulfate initiatorsand a reducing agent such as sodium hydrogen meta sulfite or sodiumhydrogen sulfite; systems based on an organic peroxide and a tertiaryamine, such as the system based on benzoyl peroxide and dimethylaniline;and systems based on an organic hydroperoxide and a transition metal,such as the system based on cumene hydroperoxide and cobalt naphthenate.

Other initiators include, but are not limited to, pinacols, such astetraphenyl-1,1,2,2-ethanediol.

Preferred heat radical initiators are selected from the group consistingof azo initiators and peroxide initiators. More preferred ones are2,2′-azobis(methyl isobutyrate), t-butyl peroxypivalate anddi(4-t-butylcyclohexyl) peroxydicarbonate, and mixtures of these.

When used in the present invention, the heat initiator is present in acatalytically effective amount, and such amount is not restricted but,typically, is about 0.01 to 5 parts by weight, preferably about 0.025 to2 parts by weight, per 100 parts by weight of the total amount of thepolymer according to the invention, which has at least one terminalacrylic functional group, and the additional monomer and oligomermixture. When a mixture of initiators is used, the total amount of theinitiator mixture is selected as if only one initiator were used.

The method of curing the heat-curable composition of the invention isnot particularly restricted. However, the temperature depends on theheat initiator used, the polymer (II), and the compound(s) added, amongothers. Generally, it is preferably within the range of 50° C. to 250°C., more preferably within the range of 70° C. to 200° C. The curingtime depends, among others, on the polymerization initiator, monomer(s),solvent and reaction temperature employed but, generally, it is withinthe range of about 1 minute to 10 hours.

<Adhesive Property Providing Agent>

In the composition of the present invention, there may be incorporated asilane coupling agent and/or an adhesive property providing agent otherthan the silane coupling agent. By adding such an adhesive propertyproviding agent, it becomes possible to reduce the risk of the sealingmaterial peeling off from adherends such as siding boards due to changesin joint width as caused by an eternal force. Further, it becomes nomore necessary in certain cases to use a primer for improving theadhesiveness, whereby the laying operation can be expected to besimplified. As specific examples of the silane coupling agent, there maybe mentioned isocyanato group-containing silanes such asγ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,γ-isocyanatopropylmethyldiethoxysilane andγ-isocyanatopropylmethyldimethoxysilane; amino group-containing silanessuch as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane,γ-(2-aminoethyl)aminopropylmethyldimethoxysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane andN-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto group-containingsilanes such as γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilaneand γ-mercaptopropylmethyldiethoxysilane; epoxy group-containing silanessuch as γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andβ-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes such asβ-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(2-methoxyethoxy)silane and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl type unsaturatedgroup-containing silanes such as vinyltrimethoxysilane,vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloxyloxypropylmethyltriethoxysilane; halogen-containing silanessuch as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such astris(trimethoxysilyl) isocyanurate. Also usable as the silane couplingagent are modified derivatives of these, for example amino-modifiedsilyl polymers, silylated amino polymers, unsaturated amino silanecomplexes, phenylamino-long chain alkylsilanes, aminosilylated siliconesand silylated polyesters.

In the practice of the invention, the silane coupling agent is usedgenerally in an amount within the range of 0.1 to 20 parts per 100 partsof the polyether polymer (I) plus vinyl polymer (II). In particular, theuse thereof within the range of 0.5 to 10 parts is preferred. If theaddition level is excessively high, the cured products obtain able bycuring the resulting curable composition may not have the desired rubberelasticity any longer, hence they can no longer function as a sealingmaterial in certain instances. When it is added to a two-componentsystem, as mentioned later herein, it is preferred that the sum of theamounts added to both components be within the range mentioned above. Asfor the effect of the silane coupling agent added to the curablecomposition of the present invention, it produces marked adhesiveproperty improving effects under non-primer or primer-treated conditionswhen the composition is applied to various adherend materials, namelyinorganic materials such as glass, aluminum, stainless steel, zinc,copper and mortar, or organic materials such as polyvinyl chloride,acrylics, polyesters, polyethylene, polypropylene and polycarbonates.When it is used under non-primer conditions, the improving effects onthe adhesion to various adherends are particularly remarkable.

Specific examples of the agent other than the silane coupling agentinclude, but are not particularly limited to, epoxy resins, phenolresins, sulfur, alkyl titanates and aromatic polyisocyanates, amongothers.

The adhesive property providing agents-specifically mentioned above maybe used singly or two or more of them may be used in admixture. Byadding these adhesive property providing agents, it is possible toimprove the adhesion to adherends.

<Plasticizers>

If necessary, any of various plasticizers may be used in the curablecomposition of the present invention. Such plasticizer is notparticularly restricted but, according to the purpose of addition, forexample adjustment of physical properties and/or modification of otherproperties, use can be made of one or a mixture of two or more ofphthalate esters such as dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl) phthalate and butyl benzyl phthalate; nonaromaticdibasic carboxylic acid esters such as dioctyl adipate, dioctylsebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters suchas butyl oleate and methyl acetylricirinolate; polyalkylene glycolesters such as diethylene glycol dibenzoate, triethylene glycoldibenzoate and pentaerythritol esters; phosphate esters such astricresyl phosphate and tributyl phosphate; trimellitates; polystyrenessuch as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene,polyisobutylene, butadiene-acrylonitrile copolymers, polychloroprene;chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls andpartially hydrogenated terphenyl; process oils; polyethers such aspolyethylene glycol, polypropylene glycol, polytetramethylene glycol andlike polyether polyols and derivatives of these polyether polyols asresulting from conversion of hydroxyl groups thereof to ester, etherand/or like groups; epoxy plasticizers such as epoxidized soybean oiland benzyl epoxystearate; polyester plasticizers obtain able from adibasic acid, such as sebacic acid, adipic acid, azelaic acid orphthalic acid, and a dihydric alcohol, such as ethylene glycol,diethylene glycol, triethylene glycol, propylene glycol or dipropyleneglycol; and vinyl polymers obtain able by polymerizing a vinylmonomer(s) by various methods, typically acrylic plasticizers, amongothers, although these are not always necessary. It is also possible toincorporate these plasticizers in the process of polymer production.

The above-mentioned acrylic plasticizers are not particularly restrictedbut include, among others, conventional ones obtain able by solutionpolymerization and solventless acrylic polymers. The latter acrylicplasticizers are more suited for the purpose of the present inventionsince they are produced by high-temperature continuous polymerizationtechniques (U.S. Pat. No. 4,414,370, Japanese Kokai PublicationSho-59-6207, Japanese Kokoku Publication Hei-05-58005, Japanese KokaiPublication Hei-01-313522, U. S. Pat. No. 5,010,166), without using anysolvent or chain transfer agent. Examples thereof are not particularlyrestricted but include, among others, UP series products (Toagosei Co.,Ltd.) (cf. Kogyo Zairyo (Magazine for Engineering Materials), October1999 issue).

The level of addition of the plasticizer, when this is used, is notparticularly restricted but generally is 5 to 150 parts by weight,preferably 10 to 120 parts by weight, more preferably 20 to 100 parts byweight, per 100 parts by weight of the sum of the polyether polymer (I)and vinyl polymer (II). At levels below 5 parts by weight, the effectsas the plasticizer are no more produced and, at levels above 150 partsby weight, the mechanical strength of the cured products becomesinsufficient.

<Fillers>

If necessary, any of various fillers may be used in the curablecomposition of the present invention. The filler is not particularlyrestricted but includes, among others, reinforcing fillers such as woodflour, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica,walnut shell flour, rice hull flour, graphite, diatomaceous earth, terraalba, fumed silica, precipitated silica, crystalline silica, fusedsilica, dolomite, silicic anhydride, hydrous silicic acid and carbonblack; fillers such as heavy calcium carbonate, colloidal calciumcarbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay,talc, titanium oxide, bentonite, organic bentonite, ferric oxide,aluminum fine particle, flint powder, zinc oxide, activated zinc white,powdered zinc and Shirasu balloons; and fibrous fillers such asasbestos, and glass fibers or filaments. Preferred among these fillersare precipitated silica, fumed silica, crystalline silica, fused silica,dolomite, carbon black, calcium carbonate, titanium oxide, talc and thelike. In particular when high strength cured products are to be obtainedusing these fillers, a filler selected from among fumed silica,precipitated silica, silicic anhydride, hydrous silicic acid, carbonblack, surface-treated fine calcium carbonate, crystalline silica, fusedsilica, calcined clay, clay and activated zinc white, among others, maybe mainly added.

When low-strength high-elongation cured products are desired, a fillerselected from among titanium oxide, calcium carbonate, talc, ferricoxide, zinc oxide and Shirasu balloons may be mainly added. Generally,when its specific surface area is small, calcium carbonate may fail toproduce sufficient improving effects on the breaking strength,elongation at break, adhesiveness and weather-resistant adhesion ofcured products. With the increasing specific surface area, its improvingeffects on the breaking strength, elongation at break, adhesiveness andweather-resistant adhesion of cured products increase.

Further, those species of calcium carbonate which have beensurface-treated with a surface-finishing agent are more preferred. Whensurface-treated calcium carbonate is used, the workability of thecurable composition of the present invention and the improving effectson the adhesiveness and weather-resistant adhesion of the curablecomposition are expected to be improved as compared with the use ofnon-surface-treated calcium carbonate. Usable as the abovesurface-treating agent are organic materials or various surfactants,such as fatty acids, fatty acid soaps and fatty acid esters, and variouscoupling agents, such as silane coupling agents and titanate couplingagents. Specific examples include, but are not limited to, fatty acidssuch as caproic acid, caprylic acid, pelargonic acid, capric acid,undecanoic acid, lauric acid, myristic acid, palmitic acid, stearicacid, behenic acid and oleic acid, the sodium, potassium or like saltsof such fatty acids, and alkyl esters of such fatty acids. Typicalexamples of the surfactants are sulfate ester type anionic surfactantssuch as polyoxyethylene alkyl ether sulfate esters and long-chainalcohol sulfates and the sodium, potassium or like salts thereof, andsulfonic acid type anionic surfactants such as alkylbenzenesulfonicacids, alkylnapthalenesulfonic acids, paraffinsulfonic acids,α-olefinsulfonic acids, alkylsulfosuccinic acids and the like and thesodium, potassium or like salts thereof. This surface-finishing agent isused in the treatment preferably in an amount within the range of 0.1 to20% by weight, more preferably within the range of 1 to 5% by weight,relative to calcium carbonate. When the amount used for the treatment isless than 0.1% by weight, the workability, adhesiveness andweather-resistant adhesion may not be improved to a sufficient extent.When it exceeds 20% by weight, the storage stability of the curablecomposition may decrease.

<Addition Level>

When a filler is used, the level of addition thereof is preferablywithin the range of 5 to 1,000 parts by weight, more preferably withinthe range of 20 to 500 parts by Weight, most preferably within the rangeof 40 to 300 parts by weight, per 100 parts by weight of the sum of thepolyether polymer (I) and vinyl polymer (II). When the addition level isbelow 5 parts by weight, the improving effects on the breaking strength,elongation at break, adhesiveness and weather-resistant adhesion may beinsufficient and, when it exceeds 1,000 parts by weight, the workabilityof the curable composition may decrease in certain instances. A singlefiller may be used alone or two or more fillers may be used incombination.

<Physical Property Modifiers>

One or more physical property modifiers may be added to the curablecomposition of the present invention according to need for adjusting thetensile characteristics of the resulting cured products.

The physical property modifier is not particularly restricted butincludes, among others, alkylalkoxysilanes such asmethyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilaneand n-propyltrimethoxysilane; functional group-containing alkoxysilanes,for example alkylisopropenoxysilanes such asdimethyldiisopropenoxysilane, methyltriisopropenoxysilane andγ-glycidoxypropylmethyldiisopropenoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane,vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)aminopropylmethyldimethoxysilane,γ-mercaptopropyltrimethoxysilane andγ-mercaptopropylmethyldimethoxysilane; silicone varnishes; andpolysiloxanes. By using such physical property modifier(s) it becomespossible to increase or decrease the hardness and/or attain elongationproperties at the time of curing of the composition of the presentinvention. The physical property modifies such as mentioned above may beused singly or two or more of them may be used in combination.

<Thixotropy Providing Agent (Antisagging Agent)>

A thixotropy providing agent (antisagging agent) may be added to thecurable composition of the present invention according to need forsagging prevention and workability improvement.

The antisagging agent is not particularly restricted but includes, amongothers, polyamide waxes; hydrogenated castor oil and derivativesthereof; and metal soaps such as calcium stearate, aluminum stearate andbarium stearate. These thixotropy providing agents (antisagging agents)may be used singly or two or more of them may be used in combination.

Other Additives

Where necessary, one or more of various additives may be added to thecurable composition of the present invention for the purpose ofadjusting various physical properties of the curable composition and/orcured products. As examples of such additives, there may be mentioned,among others, flame retardants, curability adjusting agents,antioxidants, radical inhibitors, ultra violet absorbers, metaldeactivators, antiozonants, light stabilizers, phosphorus-containingperoxide decomposers, lubricants, pigments, foaming or blowing agents,antifungal agents, rust preventives, and photocurable resins. Thesevarious additives may be used singly or two or more species may be usedin combination.

Specific examples of these additives are described, for example, inJapanese Kokoku Publication Hei-04-69659, Japanese Kokoku PublicationHei-07-108928, Japanese Kokai Publication Sho-63-254149 and JapaneseKokai Publication Sho-64-22904.

The curable composition of the present invention may be prepared as aone-pack formulation by compounding all the ingredients in advance andstoring the resulting compound in a tightly closed container, whichformulation, when applied, undergoes curing by atmospheric moisture, oras a two-pack formulation by separately compounding a curing catalyst,filler, plasticizer, water and other ingredients in advance. In thelatter case, the compound is admixed with the polymer composition priorto use. In the case of such two-pack formulation, a colorant can beadded in the step of mixing the two components and thus it becomespossible to prepare a rich assortment of colors with limited stocks inproviding sealing materials matched in color to the color of sidingboards, for instance. Thus, two-pack formulations make it easy to copewith the market demand for multicolor systems, hence are more preferredfor use in low-rise buildings or the like. The colorant, when prepared,for example in the form of a paste by blending a pigment andplasticizer, optionally together with a filler, facilitates theapplication work. Further, by adding a retarder in blending the twocomponents together, it is possible to exactly adjust the curing rate atthe site of application.

<<Cured Products>>

It is preferred that cured products not thicker than 100 μm as obtainedby curing, without adding any filler or like additive, the curablecomposition according to the invention which comprises the polyetherpolymer (I), vinyl polymer (II) and compatibilizing agent (IV) show alevel of weatherability not shorter than 20 hours in sunshineweatherometer testing.

In the practice of the present invention, the weatherability of eachcured product not thicker than 100 μm is evaluated by visual observationof the cured product surface. That the weatherability is not shorterthan 20 hours, for instance, means that the initial good surfacecondition is maintained for not shorter than 20 hours without showingsurface waviness or flatting out due to polymer elution, cracking,discoloration (in the case of colored products), chalking or otherchanges.

In the practice of the present invention, the weatherability testingrefers to the WS type test according to JIS A 1415.

<Uses>

The curing composition of the present invention can be used in variousfields of application which include, but are not limited to, sealingmaterials, for example sealing materials such as elastic sealingmaterials for building and construction and sealing materials forlaminated glass, electric and electronic part materials such as solarcell back sealers, electric insulating materials such as wire/cableinsulating sheath, pressure sensitive adhesive materials, adhesives,elastic adhesives, paints, powder paints, coating compositions, foamedbodies, potting materials for electric and electronic use, films,gaskets, casting materials, various molding materials, and rustproof andwaterproof sealants for end faces (cut sections) of net glass orlaminated glass.

BEST MODES FOR CARRYING OUT THE INVENTION

In the following, specific examples according to the present inventionand comparative examples are given to illustrate the present invention.The following examples are, however, by no means limitative of the scopeof the present invention.

In the following examples and comparative examples, “part(s)” and “%”mean “part(s) by weight” and “% by weight”, respectively.

In the following examples, the “number average molecular weigh” and“molecular weight distribution (ratio of weight average molecular weightto number average molecular weight)” were calculated by the standardpolystyrene equivalent method using gel permeation chromatography (GPC).The GPC column used was one packed with crosslinked polystyrene in a gelform (Shodex GPC K-804; product of Showa Denko) and the GPC solvent usedwas chloroform.

Synthesis Example 1 Synthesis of a Crosslinkable silyl Group-Terminatedpoly(n-butyl acrylate/stearyl acrylate) copolymer

A 2-liter flask was charged with 8.39 g (58.5 mmol) of cuprous bromideand 112 mL of acetonitrile, and the contents were heated at 70° C. withstirring under a nitrogen stream for 20 minutes. Thereto were added 17.6g (48.8 mmol) of diethyl 2,5-dibromoadipate, 996 mL (6.94 mol) of butylacrylate and 279 g (0.858 mol) stearyl acrylate, and the mixture wasfurther heated at 70° C. for 40 minutes with stirring. Thereto was added0.41 mL (1.95 mmol) of pentamethyldiethylenetriamine (herein afterreferred to as “triamine”) to thereby initiate the reaction. Then,heating at 70° C. was continued with stirring, and 2.05 mL (9.75 mmol)of triamine was added. At 330 minutes after the start of the reaction,288 mL (1.95 mol) of 1,7-octadiene and 4.1 mL (19.5 mmol) of triaminewere added, and heating at 70° C. was continued with stirring. At 570minutes after the start of the reaction, the heating was stopped. Thereaction mixture was diluted with toluene and then filtered, and thefiltrate was treated by heating under reduced pressure to give a polymer(polymer [1]). The polymer [1] obtained had a number average molecularweight of 28,800 as determined by GPC (mobile phase: chloroform;calculated on the polystyrene equivalent basis) with a molecular weightdistribution of 1.33. The number of alkenyl groups per polymer moleculeas determined by ¹H-NMR spectrometry was 2.9.

In a nitrogen atmosphere, a 2-liter flask was charged with the polymerobtained in the above manner, 17.2 g (0.175 mol) of potassium acetateand 700 mL of DMAc, and the contents were heated at 100° C. withstirring for 10 hours. The DMAc was removed from the reaction mixture byheating under reduced pressure, toluene was added, and the mixture wasfiltered. The filtrate was deprived of the volatile matter by heatingunder reduced pressure and then charged into a 2-liter flask, anadsorbent (100 g, 1:1 mixture of Kyowaad 500SN and Kyowaad 700SN,products of Kyowa Chemical) was added, and the mixture was heated at130° C. with stirring under a nitrogen stream for 9 hours. Afterdilution with toluene and removal of the adsorbent by filtration, thetoluene was distilled off from the filtrate under reduced pressure togive a polymer (polymer [2]).

A one-liter pressure reaction vessel was charged with the polymer [2](700 g), dimethoxymethylhydrosilane (26.1 mL, 0.212 mol), methylorthoformate (7.71 mL, 0.0705 mol) andplatinum(0)-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex. Theamount of the platinum catalyst used was such that the mole ratiothereof to the alkenyl group in the polymer amounted to 9×10⁻³equivalents. The mixture was heated at 100° C. for 195 minutes withstirring. The volatile matter was then distilled off from the mixtureunder reduced pressure, whereby a silyl group-terminated polymer(polymer [3]) was obtained. The polymer obtained had a number averagemolecular weight of 35,900 as determined by GPC (on the polystyreneequivalent basis) with a molecular weight distribution of 1.9. Theaverage number of the silyl groups introduced per polymer molecule asdetermined by ¹H-NMR spectrometry was 2.1.

Synthesis Example 2 Synthesis of a Crosslinkable silyl Group-Terminatedpoly(n-butyl acrylate)

A 2-liter flask was charged with 8.39 g (58.5 mmol) of cuprous bromideand 112 mL of acetonitrile, and the contents were heated at 70° C. withstirring under a nitrogen stream for 30 minutes. Thereto were added 17.6g (48.8 mmol) of diethyl 2,5-dibromoadipate and 224 mL (1.56 mol) ofbutyl acrylate, and the mixture was further heated at 70° C. withstirring for 45 minutes. Thereto was added 0.41 mL (1.95 mmol) ofpentamethyldiethylenetriamine (herein after referred to as “triamine”),and the reaction was thereby started. While continued heating at 70° C.with stirring, 895 mL (6.24 mol) of butyl acrylate was added dropwiseintermittently over 160 minutes beginning at 80 minutes after start ofthe reaction. During this dropping, 1.84 mL (8.81 mmol) of triamine wasadded. After the lapse of 375 minutes after start of the reaction, 288mL (1.95 mol) of 1,7-octadiene and 4.1 mL (19.5 mmol) of triamine wereadded, and the heating at 70° C. with stirring was further continued. At615 minutes after start of the reaction, the heating was stopped. Thereaction mixture was diluted with toluene and filtered, and the filtratewas heated under reduced pressure to give a polymer (polymer [4]). Thepolymer [4] had a number average molecular weight of 24,100 asdetermined by GPC (mobile phase: chloroform; on the polystyreneequivalent basis) with a molecular weight distribution of 1.27. Thenumber of alkenyl groups as determined by ¹H-NMR spectrometry was 2.6per polymer molecule.

In a nitrogen atmosphere, a 2-liter flask was charged with thethus-obtained polymer, 11.9 g (0.121 mol) of potassium acetate and 900mL of DMAc, and the mixture was heated at 100° C. with stirring for 11hours. The DMAc was removed by heating the reaction mixture underreduced pressure, toluene was added, and the mixture was filtered. Anadsorbent (200 g, Kyowaad 700PEL, product of Kyowa Chemical) was addedto the filtrate, and the mixture was heated at 100° C. with stirringunder a nitrogen stream for 3 hours. The adsorbent was filtered off, andthe toluene was distilled off from the filtrate under reduced pressureto give a polymer (polymer [5]).

A one-liter pressure reaction vessel was charged with the polymer [5](648 g), dimethoxymethylhydrosilane (25.5 mL, 0.207 mol), methylorthoformate (7.54 mL, 0.0689 mol) andplatinum(0)-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex. Theamount of the platinum catalyst used was such that the mole ratiothereof to the alkenyl group in the polymer amounted to 3×10⁻³equivalents. The mixture was heated at 100° C. with stirring for 2hours. The volatile matter was then distilled off from the mixture underreduced pressure, whereby a silyl group-terminated vinyl polymer(polymer [6]) was obtained. The polymer obtained had a number averagemolecular weight of 29,600 as determined by GPC (on the polystyreneequivalent basis) with a molecular weight distribution of 1.9. Theaverage number of the silyl groups introduced per polymer molecule asdetermined by ¹H-NMR spectrometry was 1.9.

Examples 1 to 5

The crosslinkable silyl group-containing vinyl polymer of SynthesisExample 1 was blended with a commercially available, crosslinkable silylgroup-terminated polyether polymer (S203, product of Kaneka Corporation)in various mixing ratios shown in Table 1, and the mixtures wereevaluated for compatibility by visual observation. Each mixture (100parts by weight) was blended under stirring with 1 part by weight ofwater and 1 part by weight of dibutyltin dimethoxide, the whole mixturewas defoamed at room temperature using a vacuum drier, and then curingwas allowed to proceed at 50° C. for 3 days to give a rubber-like curedproduct. The results thus obtained are shown in Table 1.

Comparative Examples 1 to 5

Compatibility observations were made and cured products were obtained inthe same manner as in Examples 1 to 5 except that the polymer obtainedin Synthesis Example 2 was used in lieu of the polymer obtained inSynthesis Example 1. The results are also shown in Table 1.

TABLE 1 Example Comparative Example 1 2 3 4 5 1 2 3 4 5 Vinyl polymer of10 30 50 70 90 — — — — — Synthesis Example 1 Vinyl polymer of — — — — —10 30 50 70 90 Synthesis Example 2 Polyether polymer 90 70 50 30 10 9070 50 30 10 Compatibility ◯ ◯ ◯ ◯ ◯ x x x x x Curing product ◯ ◯ ◯ ◯ ◯ xx x x x homogeneity

Blending of the polymer of Synthesis Example 1 with the polyetherpolymer gave homogeneous mixtures, and the mixtures gave homogeneouscured products. On the contrary, blending of the polymer of SynthesisExample 2 with the polyether polymer gave nonhomogeneous mixtures, andthe mixtures gave only nonhomogenous cured products.

Example 6

A commercially available, crosslinkable silyl group-containing polyetherpolymer (S303; Kaneka Corporation; 70 parts) was mixed, under stirring,with 30 parts of the crosslinkable silyl group-containing vinyl polymerof Synthesis Example 1. This polymer mixture (100 parts) was mixed,under stirring, with 120 parts of calcium carbonate (Hakuenka CCR;product of Shiraishi Calcium), 20 parts of titanium oxide (TIPAQUER-820; Ishihara Sangyo), 55 parts of a plasticizer (DIDP; DaihachiChemical Industry), 2 parts of an antisagging agent (DISPARLON #6500;Kusumoto Chemicals), 1 part of an ultra violet absorber (TINUVIN 327;Ciba Specialty Chemicals), 1 part of a light stabilizer (LS-770; SankyoOrganic Chemicals), 2 parts of a dehydrating agent (A-171 (VTMO); NipponUnicar), 3 parts of an adhesiveness providing agent (A-1120 (DAMO);Nippon Unicar) and 2 parts of a curing catalyst (U-220; Nitto Kasei),and the same test specimens as those for H tensile bond strength testingaccording to JIS A 5758 were prepared and subjected to 2 days of indoorcuring and 3 days of curing at 50° C. to give cured products.

Comparative Example 6

Cured products were produced in the same manner as in Example 6 exceptthat 100 parts of a commercially available, crosslinkable silylgroup-containing polyether polymer (S303; Kaneka Corporation) was usedin lieu of 100 parts of the polymer mixture used in Example 6.

No. 2 (1/3) dumbbell test specimens (JIS K 7113) were punched out fromthe cured products obtained in Example 6 and Comparative Example 6 andmeasured for breaking strength (Tb) and elongation at break(Eb) using aShimadzu autograph (measurement environment: 23° C., rate of pulling:200 mm/min). The results are shown in Table 2.

TABLE 2 Formulation Comparative Name Particulars Example 6 Example 6Polyether polymer S-303 70 100 Vinyl polymer Synthesis 30 — Example 1Calcium carbonate CCR 120 120 Titanium oxide TIPAQUE R-820 20 20Plasticizer DIDP 55 55 Antisagging agent DISPARLON #6500 2 2 Ultravioletabsorber TINUVIN 327 1 1 Light stabilizer LS-770 1 1 Dehydrating agentA-171(VTMO) 2 2 Adhessiveness A-1120(DAMO) 3 3 providing agent Curingcatalyst U-220 2 2 Total 306 306 Mechanical property test resultsTb(MPa) 1.47 1.77 Eb(%) 440 430

Even when the vinyl polymer of Synthesis Example 1 was blended with thepolyether polymer, cured products comparable in mechanical propertiescould be obtained.

Synthesis Example 3 Synthesis of Compatibilizing Agent [1]

A 50-mL flask was charged with 0.300 g (2.09 mmol) of cuprous bromideand 3.00 mL of acetonitrile, and the contents were heated at 70° C. withstirring under a nitrogen stream for 40 minutes. Thereto were added0.778 mL (6.98 mmol) of methyl 2-propionate, 10.0 mL (69.6 mmol) ofbutyl acrylate and 14.1 mL (69.6 mmol) of methoxydipropylene glycolacrylate, and the mixture was further heated at 70° C. with stirring for30 minutes. Thereto was added 0.07 mL (0.35 mmol) ofpentamethyldiethylenetriamine (herein after referred to as “triamine”),and the reaction was thereby started. While continued heating at 70° C.with stirring, 0.35 mL (1.75 mmol) of triamine was added. After thelapse of 290 minutes after start of the reaction, the temperature wasraised to 90° C. and the heating with stirring was further continued for70 minutes. The reaction mixture was diluted with toluene and filtered,and the filtrate was heated under reduced pressure to give acompatibilizing agent (compatibilizing agent. [1]). The compatibilizingagent [1] obtained had a number average molecular weight of 3,870 asdetermined by GPC (mobile phase: chloroform; on the polystyreneequivalent basis) with a molecular weight distribution of 1.17.

Synthesis Example 4 Synthesis of Compatibilizing Agent [2]

A compatibilizing agent (compatibilizing agent [2]) was obtained in thesame manner as in Synthesis Example 3 except that the amount of butylacrylate was 6.00 mL (41.9 mmol) and the amount of methoxydipropyleneglycol acrylate was 19.7 mL (97.7 mmol). The compatibilizing agent [2]obtained had a number average molecular weight of 3,790 as determined byGPC (mobile phase: chloroform; on the polystyrene equivalent basis) witha molecular weight distribution of 1.18.

Synthesis Example 5 Synthesis of Compatibilizing Agent [3]

A compatibilizing agent (compatibilizing agent [3]) was obtained in thesame manner as in Synthesis Example 3 except that the amount of butylacrylate was 2.00 mL (14.0 mmol) and the amount of methoxydipropyleneglycol acrylate was 25.3 mL (126 mmol). The compatibilizing agent [3]obtained had a number average molecular weight of 3,620 as determined byGPC (mobile phase: chloroform; on the polystyrene equivalent basis) witha molecular weight distribution of 1.17.

Examples 7 to 9

The crosslinkable silyl group-containing vinyl polymer of SynthesisExample 2 was blended with a commercially available, crosslinkable silylgroup-containing polyether polymer (S203HE, product of KanekaCorporation) and one of the compatibilizing agents [1] to [3] in themixing ratio shown in Table 3, and the mixtures were evaluated forcompatibility by visual observation. Each mixture (100 parts by weight)was blended under stirring with 1 part by weight of water and 1 part byweight of dibutyltin dimethoxide, the whole mixture was degassed at roomtemperature using a vacuum drier, and then curing was allowed to proceedat 50° C. for 3 days to give a rubber-like cured product. The resultsthus obtained are shown in Table 3.

Comparative Example 7

A compatibility observation was made and a cured product was obtained inthe same manner as in Examples 7 to 9 except that the compatibilizingagent was not used. The results are also shown in Table 3.

TABLE 3 Comparative Example 7 Example 8 Example 9 Example 3 Vinylpolymer of 30 30 30 30 Synthesis Example 2 Polyether polymer 70 70 70 70(S203HE) Compatibilizer[1] 10 — — — Compatibilizer[2] — 10 — —Compatibilizer[3] — — 10 — Compatibility ◯ ◯ ◯ X Curing product ◯ ◯ ◯ Xhomogeneity

Blending of the mixture of the polyether polymer and the vinyl polymerof Synthesis Example 2 with the compatibilizing agents gave homogeneousmixtures, and the mixtures gave homogeneous cured products. On thecontrary, nonhomogeneous mixtures were obtained without using anycompatibilizing agent, and the mixtures gave only nonhomogenous curedproducts.

Synthesis Example 6

A 50-L reaction vessel equipped with a reflux column and a stirrer wascharged with a suspension of CuBr (251.82 g, 1.76 mol) in acetonitrile(2,640 g), the reactor inside was sealed with nitrogen, and the contentswere then stirred at 65° C. for 30 minutes. Thereto were added butylacrylate (6.0 kg), diethyl 2,5-dibromoadipate (526.70 g, 1.46 mol),acetonitrile (695 g) and pentamethyldiethylenetriamine (herein afterreferred to as “triamine”) (12.0 mL, 58.5 mmol) to thereby initiate thereaction. While heating at 80° C. with stirring, butyl acrylate (24.0kg) was continuously added dropwise. During the dropping of butylacrylate, triamine (36.0 mL, 176 mmol) was added. Then, while continuedheating at 80° C. with stirring, 1,7-octadiene (6.448 kg) and triamine(120.0 mL, 585 mmol) were added. The resulting mixture was furtherheated at 80° C. with stirring for 4 hours. Then, the heating withstirring was once discontinued, triamine (80.0 mL, 390 mmol) was added,and the mixture was heated at 90° C. with stirring for 4 hours to give areaction mixture containing a polymer (polymer [1]) (polymerizationreaction mixture [1′]).

The polymer [1] had a number average molecular weight of 23,600 asdetermined by GPC (on the polystyrene equivalent basis) with a molecularweight distribution of 1.21. The average number of alkenyl groupsintroduced per polymer molecule was 2.9 as determined by ¹H NMRanalysis.

Example 10

A curable composition was prepared by thoroughly blending 50 parts ofthe polymer [1] obtained in Synthesis Example 6 and 50 parts of acommercially available, crosslinkable silyl group-containing polyetherpolymer (S203, product of Kaneka Corporation) with a compatibilizingagent (DIDP (diisodecyl phthalate), product of Kyowa Hakko).

Comparative Example 8

A curable composition was prepared in the same manner as in Example 10except that the compatibilizing agent was not added.

Evaluation 1

The curable compositions obtained in Example 10 and Comparative Example8 were respectively placed in glass bottles and, after sealing, allowedto stand at room temperature (15 to 23° C.) for 1 day and, then,observed for their conditions. The curable composition of Example 10showed compatibility without any boundary face being confirmed uponvisual observation whereas a boundary line was confirmed by visualobservation with the curable composition of Comparative Example 8.

Example 11

One part of a tetravalent tin catalyst (dibutyltin diacetylacetonate)was thoroughly admixed with 100 parts of the curable composition ofExample 10, and the blend was poured into an aluminum mold (about 80mm×about 60 mm×about 2 mm) and allowed to stand at room temperature for2 days and then at 50° C. for 3 days to give a sheet-like cured product.

Comparative Example 9

One part of a tetravalent tin catalyst (dibutyltin diacetylacetonate)was thoroughly admixed with 100 parts of the curable composition ofComparative Example 8, and the blend was poured into an aluminum mold(about 80 mm×about 60 mm×about 2 mm) and allowed to stand at roomtemperature for 2 days and then at 50° C. for 3 days to give asheet-like cured product.

Evaluation 2

No. 2 (1/3) dumbbell test specimens (JIS K 7113) were punched out fromthe cured products obtained in Example 11 and Comparative Example 9 andmeasured for elongation at break (Eb) using a Shimadzu autograph(measurement environment: 23° C., rate of pulling: 200 mm/min). Theresults are shown in Table 4. A higher elongation was obtained inExample 11 as compared with Comparative Example 9.

TABLE 4 Eb(%) Example 11 390 Comparative 330 Example 9

Example 12

One part of a tetravalent tin catalyst (dibutyltin diacetylacetonate)was thoroughly admixed with 100 parts of the curable composition ofExample 10, and the blend was applied to an about 100-μm-thick aluminumsheet and allowed to stand at room temperature for 2 days and then at50° C. for 3 days to give a cured product.

Comparative Example 10

One part of a tetravalent tin catalyst (dibutyltin diacetylacetonate)was thoroughly admixed with 100 parts of the curable composition ofComparative Example 8, and the blend was applied to an about100-μm-thick aluminum sheet and allowed to stand at room temperature for2 days and then at 50° C. for 3 days to give a cured product.

Evaluation 3

The cured products obtained in Example 12 and Comparative Example 10were tested for weatherability using a sunshine weatherometer (Suga TestInstruments model WEL-SUN-DC, black panel temperature 63° C., 18 minutesof raining per 2 hours of irradiation). After the predetermined periodof weatherability testing, the surface condition of each product wasobserved. The cured product of Example 12 was observed for surfacecondition after 20 hours and 48 hours of irradiation in the sunshineweatherometer. The results are shown in Table 5.

TABLE 5 After 20 hours of After 48 hours of weathering testingweathering testing Example 12 ◯ Δ Comparative X — Example 10 ◯: Nochange. Δ: Slight change in form. X: Dissolution occurred and theoriginal form was lost.

INDUSTRIAL APPLICABILITY

The curable composition of the present invention, which has theabove-mentioned constitution, is excellent in storage stability, givescured products high in gel fraction and elongation, excellent inweatherability, among others, and uniform in appearance.

1. A curable composition which comprises the following three components:(I) a polyether polymer having at least one crosslinkable functionalgroup, (II) a vinyl polymer incompatible with said polyether polymer andhaving at least one crosslinkable function group, and (IV) at least onecompatibilizing agent capable of compatibilizing said polyether polymerand said vinyl polymer with each other when added to a mixture thereof,said compatibilizing agent being selected from the group consisting ofnonpolymer organic compounds, polymers obtain able by polymerizing amonomer or monomers other than vinyl monomers, and polymers obtain ableby polymerizing a single vinyl monomer.
 2. The curable compositionaccording to 1 wherein the compatibilizing agent (IV) is apolyoxyalkylene having a molecular weight of not more than 3,000.
 3. Thecurable composition according to claim 2, wherein the compatibilizingagent (IV) is polypropylene oxide having a molecular weight of not morethan 3,000.
 4. The curable composition according to 4, in which thecured product derived there from by curing without using any filler andhaving a thickness of not more than 100 μm shows a level ofweatherability which is not shorter than 20 hours in sunshineweathermeter testing.
 5. A compatibilizing agent obtain able bycopolymerization of a plurality of vinyl monomers and capable ofcompatibilizing the two components: (I) a polyether polymer having atleast one crosslinkable functional group, and (II) a vinyl polymerincompatible with said polyether polymer and having at least onecrosslinkable function group, with each other, when added to a mixturethereof.
 6. The compatibilizing agent according to claim 5, which isobtain able by the copolymerization of at least one vinyl monomerselected from among the monomers usable in polymerizing the vinylpolymer (II), with another vinyl monomer.
 7. The compatibilizing agentaccording to claim 6, wherein the other vinyl monomer is a vinyl monomerhaving a polyether structure.
 8. The compatibilizing agent according toclaim 7, wherein the mole ratio between the at least one monomerselected from among the monomers usable in polymerizing the vinylpolymer (II) and the vinyl monomer having a polyether structure iswithin the range of 1:20 to 20:1.
 9. The compatibilizing agent accordingto 5, which has a number average molecular weight of 500 to 50,000 asdetermined by gel permeation chromatography.
 10. The compatibilizingagent according to 7, wherein the polyether structure is essentiallypolypropylene oxide.
 11. The compatibilizing agent according to 5wherein the vinyl monomer is a (meth)acrylic monomer.
 12. Thecompatibilizing agent according to 7, which is produced by a livingradical polymerization technique.
 13. The compatibilizing agentaccording to claim 12, wherein the living radical polymerizationtechnique consists in atom transfer radical polymerization.
 14. Thecompatibilizing agent according to 6, which has a number averagemolecular weight of 500 to 50,000 as determined by gel permeationchromatography.
 15. The compatibilizing agent according to 7, which hasa number average molecular weight of 500 to 50,000 as determined by gelpermeation chromatography.
 16. The compatibilizing agent according to 8,which has a number average molecular weight of 500 to 50,000 asdetermined by gel permeation chromatography.
 17. The compatibilizingagent according to 8, wherein the polyether structure is essentiallypolypropylene oxide.
 18. The compatibilizing agent according to 9,wherein the polyether structure is essentially polypropylene oxide. 19.The compatibilizing agent according to 6 wherein the vinyl monomer is a(meth)acrylic monomer.
 20. The compatibilizing agent according to 7wherein the vinyl monomer is a (meth)acrylic monomer.